Complexes of 1, 8-naphthyridines with elements of the first transition series
by Ahmad Emad
A thesis submitted to the Graduate Faculty in partial fulfillment of the requirements for the degree of
DOCTOR OF PHILOSOPHY in . CHEMISTRY
Montana State University
© Copyright by Ahmad Emad (1971)
Abstract:
Twenty-three new complexes of 1,8-naphthyridine (NN) and 2,7-dimethyl-1,8-naphthyridine (dmNN)
with transition metals have been prepared and characterized. These complexes have been classified
according to the anion for purposes of discussion.
Five halide complexes, four with copper(II) and one cobalt(II) complex with NN or dmNN were
synthesized. Among these, two magnetically anomalous complexes, Cu(NN)Cl2 and Cu(NN)Br2 ,
were discovered. The possible structural geometries have been discussed.
Transition metal complexes of manganese(II), cobalt(II), nickel(II), copper(II), zinc(II), and sliver(I)
perchlorates with NN were isolated. Chelation of NN with the divalent metal ions and monodentate
coordination with silver(I) ion has been suggested.
Eight nitrate complexes of NN with the same transition elements have been prepared. Coordination of
the naphthyridine molecule was found to be similar to that of the perchlorate compounds. In several of
these complexes, coordination of the nitrate ions or water molecules is indicated by the infrared
spectra.
The chemistry of complexes of this ligand with copper(I) ion was also studied. Four copper(I)
complexes containing chloride and perchlorate anions with NN and dmNN were prepared. The possible
coordination of the ligands and complexes is discussed and tentative structures proposed. COMPLEXES OF I, 8 -NAPHTHYRIDINES WITH ELEMENTS OF THE
FIRST TRANSITION SERIES
by
AHMAD EMAD
A t h e s i s s u b m itte d to th e G ra d u a te F a c u lty in p a r tia l
fu lfillm e n t o f th e re q u ire m e n ts fo r th e d e g re e
of
DOCTOR OF PHILOSOPHY
in .
CHEMISTRY
A pproved:
h tr, M a jo r D e p a rtm e n t
C h airm an , E xam ining C om m ittee
G ra d u a te fD e a n
MONTANA STATE UNIVERSITY
B o zem an , M o n ta n a
A u g u st, 1971
ill
ACKNOWLEDGEMENT
The a u th o r w is h e s to e x p r e s s h is s in c e r e g ra titu d e to D r. K en n eth .
E m erson w ho d ir e c te d th is r e s e a r c h an d to th a n k him fo r h is a d v ic e ,
g u id a n c e an d in v a lu a b le i d e a s , b o th in e x p e rim e n ta l w ork an d in th e
c o m p o s itio n o f th is t h e s i s .
S p e c ia l th a n k s a re e x te n d e d to th o s e m em bers of. th e fa c u lty and
frie n d s w ho d ir e c tly o r in d ir e c tly e n c o u ra g e d an d a id e d ; an d to D r.
G . A. C ro s b y an d D r. H ow ard S an d b erg fo r p e rm ittin g th e a u th o r to u se.
th e C ary 14 a n d D iffu s e R e fle c ta n c e A tta c h m e n t a t W a s h in g to n S ta te
U n iv e r s ity , P u llm a n , W a s h in g to n .
TABLE OF CONTENTS
PAGE
V i t a .............................................
11
A c k n o w le d g e m e n t................................
ill
T ab le o f C o n t e n t s ............. ............................................................. ......................
Iv
L is t o f T a b le s
vi
.................... ...................... .......................................................... ...
L is t o f F i g u r e s ............................................................................................................. v iii
A b s tra c t ......................................................................
INTRODUCTION ...........................................................
R ev iew o f L ite ra tu re
ix
I
. ...............................................................................
I
I , 8 -N a p h th y rid in e s an d T h e ir C o m p le x e s ............ ..............
3
N itro g e n C o m p le x e s o f C o p p e r ( I ) ...............................
9
Aims o f T his R e s e a r c h ...................
EXPERIMENTAL...................
A n a ly tic a l T e c h n iq u e s
11
13
..........................................
13
P re p a ra tio n o f C om pounds ....................................
18
I.
H a lid e C o m p le x e s ..............
II. P e rc h lo ra te C o m p le x e s .............................................
II I. N itra te C o m p le x e s
..................................................................
IV. C opper(I) C o m p le x es
18
21
24
28
V
PAGE
RESULTS AND D ISCUSSION ...........................................................................
P a rt I
— H a lid e C o m p le x e s
. . ...........................................
P a rt II
— P e rc h lo ra te C o m p le x es
31
31
.................................................
57
P a rt III — N itra te C o m p l e x e s ..........................................................
72
P a rt IV — C opper(I) C o m p le x e s ................................................. ... .
87
A P P E N D IX ................................................................................................................
98
LITERATURE CITED
105
vi
LIST OF TABLES
TABLE
PAGE
I.
The p Kq V a lu e s o f D iffe re n t A ro m atic A m i n e s ..............................
3
II.
H a lid e C o m p o u n d s ......................................................................................
20
H I.
P e rc h lo ra te C o m p o u n d s ....................................................
23
IV.
N itra te C om pounds
27
. . , . .....................................................................
C opper(I) C o m p o u n d s .............................
30
VI.
M a g n e tic S u s c e p tib ility o f D a ta o f H a lid e C o m p le x e s . . . .
32
VII.
S e le c te d In fra re d A b so rp tio n s o f H a lid p C o m p le x e s . . . . . .
37
V.
■V iii. In fra re d A b so rp tio n s o f Some C u(II) C o m p le x es
.......................
40
V is ib le A b so rp tio n S p e c tra o f H a lid e C o m p le x e s .......................
43
E le c tro n ic A b so rp tio n S p e c tra o f Some C u(II) H a lid e s
. . . .
46
XI.
S e le c te d In fra re d A b so rp tio n s o f C u W m N N ^ X g ..........................
48
XII.
U ltr a v io le t A b so rp tio n S p e c tra o f H a lid e C o m p l e x e s .............
53
X III.
S e le c te d In fra re d A b so rp tio n s o f P e rc h lo ra te C o m p le x e s . . .
58
XIV.
D iffu se R e f le c ta n c e S p e c tra o f P e rc h lo ra te C o m p le x e s . . . .
62
XV.
E le c tro n ic A b so rp tio n S p e c tra o f P e rc h lo ra te C p rp p le x es . . .
63
C r y s ta llo g r a p h ic D a ta o f P e rc h lo ra te C o m p le x es
65
IX.
X.
XVI.
XVII.
XVIII.
....................
U ltr a v io le t A b so rp tio n S p e c tra o f P e rc h lo ra te C o m p le x e s
S e le c te d In fra re d A b so rp tio n s o f N itra te C o m p le x e s
. .
69
.............
73
XIX.
R e fle c ta n c e S p e c tra o f N itra te C o m p le x e s
XX.
In fra re d B ands o f N itra te I o n ..............................................................
77
In fra re d A b so rp tio n B ands o f Som e N itra te C o m p le x e s
78
XXI.
. . . . . . . . . . .
. . . .
76
v ii
TABLE
PAGE
XXII. U ltr a v io le t A b so rp tio n S p e c tra o f N itra te C o m p l e t e s ..............
84
XXIII.
S e le c te d In fra re d A b so rp tio n s o f C opper(I) C o m p le x e s . . . .
89
XXIV.
U ltr a v io le t A b so rp tio n S p e c tra o f C o p p er(I) C o m p le x e s
95
...
XXV. S u lfa te C o m p le x e s ..................................................................................... 103
XXVI.
A c e ta te C o m p le x e s
104
v iii
LIST OF FIGURES
FIGURE
'
PAGE
1.
H e te r o c y c lic M o le c u le s C o n ta in in g Two N itro g e n A tom s . . . .
4
2.
Bis( 1 ,8 -n a p h th y rid in e ) co p p er(II) c h lo rid e
6
3.
S tru c tu re o f T e tra k is ( 1,8 -n a p h th y rid in e (iro n (II )p e rc h lo ra te . . .
4.
S c h e m a tic D iag ram o f th e I o n - e x c h a n g e c o l u m n ............. ... . . .
5.
M a g n e tic S u s c e p ti b ilitie s o f th e S ubnorm al C o pper(II)
C o m p le x e s
8
14
....................... .......................................................................
34
6.
P o s s ib le S tru c tu re s for C u(N N )C lg a n d C u (N N )B rg .......................
35
7.
In fra re d S p e c tra o f C jq HjgN g a n d C g H g N g .......................... ... . . .
38
8.
In fra re d S p e c tra o f C u(C gH gN g)C lg a n d C ^ C g H g N g ^ C lg
• • •
39
9.
D iffu s e R e fle c ta n c e o f H a lid e C o m p le x e s
........................................
42
10.
.
...........................................
In fra re d S p e c tra o f C u (C g H g N g )^ " 4 HgO an d
C u (C 8H 6N 2) 4 (C lO 4) 2 ..................................................................................
11.
61
In fra re d S p e c tra o f C u(C gH g N 2) 2 ^g(N O g)2 an d
C u (C 8H 6N g )2 (N O 3) 2 ..................................................................................
79
1 2. In fra re d S p e c tra o f C u (C jq H jq N 2) 2 CIO4
C u(C gH gN 2)C lO 4
.................................... '...................................................
90
13.
S u g g e s te d S tru c tu re for C u(N N )C lO 4 C o m p l e x ................................
91
14.
S tru c tu re b f(C H g N = N C H g )C u g C lg C o m p o u n d .............................. .
96
ix
ABSTRACT
T w e n ty -th re e n e w c o m p le x e s o f 1 ,8 -n a p h th y rid in e (NN) and
2 ,7 - d im e th y l- l/8 -n a p h th y rid in e (drpNN) w ith tr a n s itio n m e ta ls h a v e b e e n
p re p a re d a n d c h a r a c te r iz e d . T h e se c o m p le x e s h ^ v e b e e n c l a s s i f i e d
a c c o rd in g to th e a n io n fo r p u rp o s e s o f d is c u s s io n .
F ive h a lid e c o m p le x e s , fo u r w ith c o p p e d II) an d o n e c o b a lt(II)
c o m p le x w ith NN o r dmNN w e re s y n th e s iz e d . Among t h e s e , tw o m ag­
n e tic a lly a n o m a lo u s c o m p le x e s , C u(N N )C I2 a n d Cu(NN)Brg , w ere d i s ­
c o v e re d . The p o s s ib le s tr u c tu r a l g e o m e trie s h a v e b e e n d i s c u s s e d .
T ra n s itio n m e ta l c o m n le x e s o f m a n g a n e s e (II), C o b alt(II), n ic k e l(II),
c o p p e r(II), z in c (II), a n d s liv e d I) p e r c h lo r a te s w ith NN w ere is o la te d .
C h e la tio n o f NN w ith th e d iv a le n t m e ta l io n s an d m o n o d e n ta te c o o rd in a ­
tio n w ith s ilv e r(I) io n h a s b e e n s u g g e s te d .
E ig h t n itr a te c o m p le x e s o f NN w ith th e sam e tr a n s itio n e le m e n ts
h a v e b e e n p re p a re d . C o o rd in a tio n o f th e n a p h th y rid in e m o le c u le w as
fo u n d to be s im ila r to t h a t o f th e p e rc h lo ra te c o m p o u n d s. In s e v e r a l o f
th e s e c o m p le x e s , c o o rd in a tio n o f th e n itr a te io n s o r w a te r m o le c u le s is
in d ic a te d by th e in fra re d s p e c t r a .
The c h e m is try o f c o m p le x e s o f th is lig a n d w ith c o p p er(I) io n w as
a ls o s tu d ie d . Four c o p p er(I) c o m p le x e s c o n ta in in g c h lo rid e an d p e r­
c h lo ra te a n io n s w ith NN a n d dmNN w e re p re p a re d . The p o s s ib le
c o o rd in a tio n o f th e lig a n d s a n d c o m p le x e s is d is c u s s e d an d te n ta tiv e
s tr u c tu r e s p ro p o s e d .
IN T R O D U C T IO N
REVIEW OF LITERATURE:
In r e c e n t y e a r s , th e r e h a s b e e n so m e in te r e s t in tr a n s itio n m e ta l
c o m p le x e s o f h e te r o c y c lic m o le c u le s , c o n ta in in g tw o n itro g e n a to m s ,
form ing fo u r-m e m b e re d rin g c h e la te s ( 1 ,2 ,3 ) . M o st o f th e common
c h e la tin g a g e n ts form f iv e - o r s ix -m e m b e re d rin g s an d l i t t l e is know n
a b o u t th e c h e la tin g p o w e rs o f a g e n ts form ing fo u r-m e m b e re d r i n g s . The
n itro g e n h e te r o c y c le s a b le to form fiv e -m e m b e re d rin g c h e la te s h a v e
lo n g b e e n s tu d ie d (4 ,5 ,6 ) . The e x a m p le s o f th e s e a re : 2 ,2 '- b ip y r id in e ,
1 ,1 0 -p h e n a n th ro lin e , a n d th e ir d e r i v a t i v e s . T h e se m o le c u le s a re good
rr-b o n d in g lig a n d s a n d th e ir s tro n g c r y s ta l fie ld p ro p e rtie s a re p a r tia lly
due to th e ir a b ility to p a r tic ip a te in n -b o n d in g w ith th e m e ta l a to m s (7 ).
The com pound 1 ,8 -n a p h th y rid in e an d its d e r iv a tiv e s b y c o m p a riso n form
fo u r-m e m b e re d rin g c h e la te s r a th e r th a n f iv e . Io n ic lig a n d s w h ic h form
fo u r-m e m b e re d c h e la te rin g s h a v e b e e n know n for a lo n g tim e , and th e ir
c o m p le x e s a re s ta b i liz e d by io n ic c h a r g e s . E x am p les o f t h e s e are:
p e r c h lo r a te s (8 ,9 ) , n itr a te s (10), c a r b o n a te s (11), an d c a r b o x y la te s (12).
The s im ila r ity o f c h e la te d 1 ,8 -n a p h th y rid in e c o m p le x e s to c h e la te co m ­
p le x e s o f a c e ta te io n s s u g g e s ts th a t n a p h th y rid in e s m ig h t form p o ly ­
n u c le a r c o m p le x e s w ith c o p p e r o r o th e r tr a n s itio n m e t a l s , a s a c e ta te
d o e s in a few c a s e s .
Among t h e s e a n io n ic l i g a n d s , th e c a rb o x y la te io n s h a v e b e en
m o st th o ro u g h ly s tu d ie d . T hey m ay c o o rd in a te th ro u g h o n e o r b o th
2
o x y g e n s a n d th e y a ls o form a c l a s s o f p o ly n u c le a r m o le c u le s w ith
m e ta l- m e ta l in te r a c tio n s w h e re th e c a r b o x y la te group c o o rd in a te s a s a
b id e n ta te lig a n d to tw o m e ta l a to m s . A la rg e num ber o f th e s e c o m p le x e s
h a v e b e e n in v e s tig a te d an d c h a r a c te r iz e d w ith c o p p er(II) io n s (12).
D im eric co p p er(II) c a r b o x y la te s sh o w u n u s u a l m a g n e tic p ro p e r­
t i e s . T hey e x h ib it a m a g n e tic m om ent l e s s th a n 1.7 B. M . co m p ared w ith
th e v a lu e o f 1.8-2.2 B .M . for n o rm al co p p er(II) c o m p o u n d s. The m ag ­
n e tic s u s c e p t i b i l i t y o f th e s e c o m p le x e s d o e s n o t o b e y th e C u rie -W e is s
la w . I t p a s s e s th ro u g h a m axim um a t o r n e a r room te m p e ra tu re a n d d e ­
c r e a s e s r a p id ly a s th e te m p e ra tu re is lo w e r e d . Some o f t h e s e com ­
p o u n d s h a v e a n o m a lo u s m a g n e tic p ro p e rtie s a t lo w te m p e r a tu r e , b u t
a p p e a r to be norm al a t or n e a r room te m p e r a tu r e . The in te r a c tio n b e ­
tw e e n d o r b ita ls of co p p er(II) io n s an d th e n a tu re o f th e lig a n d s are
r e s p o n s ib le fo r th e m a g n itu d e o f th is su b n o rm a l b e h a v io r . The la rg e
o v e rla p o f th e 3d o r b ita ls b e tw e e n th e c o p p er(II) io n s in th e co m p lex a s
w e ll a s th e h ig h te n d e n c y o f th e lig a n d for c o o rd in a tio n w ill s ta b iliz e
th e d im e ric s tru c tu re o f th e c o m p le x . S im ila rly th e fo rm atio n o f th e
d im e ric com pound in o rg a n ic s o lv e n ts s u c h a s a lc o h o l, e th e r , e t c . is
m ore fa v o ra b le th a n in a q u e o u s s o lu tio n . The d im e ric s tr u c tu r e is d e ­
s tro y e d in w a te r , r e s u ltin g in m o n o m eric h y d ra te d i o n s . T h is is d u e to
th e s tro n g e r c o o rd in a tio n a b ility o f w a te r co m p ared w ith t h a t o f o rg a n ic
m o le c u le s .
3
1,8-NAPHTHYRIDINES'AND THEIR COMPLEXES: — The com pound
1 ,8 -n a p h th y rid in e is a n a ro m a tic m o le c u le (F ig . I) h a v in g o n e u n s h a re d
p a ir o f e le c tr o n s on e a c h n itro g e n an d is s y m b o liz e d th ro u g h o u t th is
t h e s i s a s "NN" fo r s im p lic ity . In n a p h th y rid in e m o le c u le s th e p a irs o f
e le c tr o n s in th e n o n b o n d in g a to m ic o r b ita ls o f th e n itro g e n s a re re s p o n ­
s ib le for th e ir b a s ic p r o p e r t i e s , s in c e o v e rla p o f th is o r b i t a l , a s a
L ew is b a s e , w ith an o r b ita l o f a L ew is a c id w ill r e s u lt in a b o n d . S ub­
s titu tio n , o f tw o m e th y l g ro u p s in 1 ,8 -n a p h th y rid in e "dm NN" w o u ld be
e x p e c te d to in c r e a s e th e b a s ic ity o f th e s u b s titu te d m o le c u le a s is o b ­
s e rv e d in 1 ,1 0 -p h e n a n th ro lin e . The b a s i c i t y o f th e p a re n t p h e n a n th ro Iin e m o le c u le is lo w e r c o m p ared to th e 2,9-d im e th y l s u b s titu te d d e r iv a ­
t i v e . The p Ka v a lu e s for som e o f th e n itro g e n h e te r o c y c le s a re l i s t e d in
T ab le I , b u t th e v a lu e o f pKQ fo r 1 ,8 -n a p h th y rid in e h a s n o t b e e n re p o rte d
in th e li t e r a t u r e . In T ab le I , th e pKa v a lu e s o f d iffe re n t a ro m a tic
a m in e s a re co m p ared in w h ic h th e Ka v a lu e s a re th e d is s o c ia tio n c o n ­
s ta n t s o f p ro to n a te d am m onium io n s a t 2 5 °C in w a te r .
T ab le I
C om pound
Ref.
1,10 -p h e n a n th ro lin e
4.86
(13)
2,9- d i m e t h y l - 1,10 -p h e n a n th ro lin e
6.17
(13)
2 ,7 -d im e th y l- 1 ,8 -n a p h th y rid in e
4.50
(13)
P y rid in e
5.18
(14)
4
j— N
1,10 -P h e n a n th ro lin e
"p h en "
"dm p"
1 ,8 -N a p h th y rid in e
2 ,7 - D im e th y l- l,8 -n a p h th y rid in e
"N N "
"dmNN"
OUO
2 ,2 '-B ip y rid in e
"b ip y "
H e te r o c y c lic m o le c u le s c o n ta in in g tw o n itro g e n a to m s .
F ig u re I
5
The com pound 1,8-n a p h th y rid in e w a s p re p a re d by K o ller (15) and
by A lb ert (16) by a m u lti- s te p s e q u e n c e s ta r tin g w ith m e th y l- 2 a m in o n ic o tin a te . A llen (17) re p o rte d th e s y n th e s is o f 1 ,8 -n a p h th y rid in e
u s in g 2 -a m in o p y rid in e a s th e s ta r tin g m a te r ia l. The s y n th e s is o f 2 ,7 d ic h lo ro - 4 - m e th y l- 1 ,8 - n a p h th y r id in e from 2 ,5 -d ia m in o p y rid in e w a s r e ­
p o rte d by S ie d e (18) in 1 926. O c h ia i a n d M iy a k i (19) re p o rte d a c a ta ly tic
h y d ro g e n a tio n s c h e m e for c o n v e rs io n o f 2 ,7 - d ic h lo r o - 4 - m e th y l- 1,8n a p h th y rid in e to 4 - m e th y l- l,8 - n a p h th y r id in e . In 19 64 th e s y n th e s is o f
2 - a m i n o - 7- h y d r o x y - 1,8 - n a p h th y rid in e from 2 ,6 -d ia m in o p y rid in e w a s r e ­
p o rte d (2 0 ). E nw all (21) s y n th e s iz e d 1 ,8 -n a p h th y rid in e an d i t s 4 -m e th y l
d e r iv a tiv e by a f o u r - s te p s y n th e s is u s in g 2 ,6 -d ia m in o p y rid in e .
All th e s e p re v io u s s y n th e s e s w h ic h re q u ire a m u lti- s te p s y n th e ­
s i s p ro c e e d in a lo w y ie ld .. P a u d le r an d K ress (22, 23) re p o rte d in 1967
a o n e - s te p s y n th e s is o f 1 ,8 -n a p h th y rid in e . T hey a p p lie d th e Skraup
re a c tio n to 2 -a m in o p y rid in e u s in g m e ta -n itro b e n z e n e s u lfo n ic a c id
(s u lfo -m ix ) a s th e o x id iz in g a g e n t. The c o n d e n s a tio n o f
2 -a m in o p y rid in e e m p lo y in g s u lf o - m ix a n d g ly c e ro l g a v e
1 ,8 -n a p h th y rid in e in 30% y ie ld w h e re a s th e 2 - a m in o - 6 m e th y ln a p h th y rid in e r e a c tio n w ith c ro to n a ld e h y d e an d s u lfo -m ix p ro ­
d u c e d 2 ,7 -d im e th y l- 1 ,8 -n a p h th y rid in e in 17% y ie ld .
The f i r s t tr a n s itio n m e ta l c o m p le x w ith 1 ,8 -n a p h th y rid in e w a s
s y n th e s iz e d an d i t s s tru c tu re d e te rm in e d b y X -ra y d iff ra c tio n by E nw all
(24) in th is la b o r a to r y . E nw all (21) is o la te d C u tN N ^ C ^ an d
6
C u tN N ^ B fg . The form er w a s a g re e n c r y s ta ll in e s u b s ta n c e an d th e
l a t t e r a n o ra n g e com pound w ith a d is o rd e re d c r y s ta l s t r u c t u r e . Both
co m p o u n d s w e re c r y s ta ll iz e d o u t o f a q u e o u s s o lu tio n a n d .th e c h lo rid e
c o m p le x w a s sh o w n to h a v e a c is s q u a re p la n a r s tr u c t u r e . N a p h th y rid in e i s c o o rd in a te d th ro u g h o n e o f i t s n itr o g e n s ; th e u n c o o rd in a te d
n itro g e n s lie b e lo w a n d a b o v e th e p la n e o f th e c o m p le x .
Cl
/ \
Cl
Bis( 1,8 -n a p h th y rid in e ) co p p er(II) c h lo rid e
F ig u re 2
The c o p p e r -c h lo rid e d is ta n c e is 2 .2 5 $ , th e c o p p e r -n itro g e n d is ta n c e is
2 .0 2 $ , an d th e c o p p e r -u n c o o r d in a te d n itro g e n d is ta n c e i s 2 .7 6 $ . The
m a g n e tic s u s c e p t i b i l i t y m e a s u re m e n t o f th e co m p lex a t room te m p e ra tu re
sh o w e d th a t i t h a d a n o rm al m a g n e tic m om ent o f 1.90 B. M .
H e n d ric k e r an d R eed (13) in 19 69 re p o rte d th e p re p a ra tio n and
c h a r a c te r iz a tio n o f G roup VIb m e ta l c a rb o n y l c o m p le x e s w ith
7
2 ,7 - d im e th y l- l,8 ~ n a p h th y r id in e „ From th e in fra re d s p e c t r a , c a rb o n y l
s tr e tc h in g f r e q u e n c i e s , a n d th e ir fo rc e c o n s ta n ts c o m p ared w ith th e
fiv e -m e m b e re d rin g n itro g e n c h e la te s th e y c o n c lu d e d th a t n a p h th y rid in e
is a s lig h tly b e tte r rr-b o n d in g lig a n d .
H e n d ric k e r (2 5) re p o rte d th e dia»lkyltin d ic h lo rid e a d d u c ts o f th is
sam e lig a n d an d from th e ir in fra re d an d pm r s p e c tr a he d e c id e d th a t th e
lig a n d form s a fo u r-m e m b e re d rin g c h e la te w ith th e c e n tr a l m e ta l.
H e n d ric k e r an d B odner (2 6) is o la te d m a g n e s iu m (II), c a lc iu m ( II),
S tro n tiu m (II), a n d barium (II) p e rc h lo ra te c o m p le x e s o f 1,8-n a p h th y rid in e
a n d i t s 2 ,7 -d im e th y l d e riv a tiv e from a n h y d ro u s o rg a n ic s o l u t i o n s . Com ­
p le x e s o f 1 ,8 -n a p h th y rid in e w ere h y d r a te d , b u t c o m p le x e s o f 2,7d im e th y l- l,8 - n a p h th y r id in e w ere a n h y d ro u s e x c e p t for th e m ag n esiu m (II)
c o m p le x . The s o u rc e o f th e w a te r in h y d ra te d co m p o u n d s w a s n o t e x ­
p la in e d .
From in fra re d a n d p ro to n m a g n e tic re s o n a n c e s p e c tr a th e y
c o n c lu d e d th a t a ll w e re c h e la te d w ith n a p h th y rid in e th ro u g h b o th n itr o ­
g e n s an d th e p e r c h lo r a te s w e re a ll c o o rd in a te d to th e c e n tr a l m etal
e x c e p t in M g fd m N N ^ C lO ^ g ' 3.5 HgO w h e re w a te r m o le c u le s w ere
c o o rd in a te d to th e m e ta l in s te a d o f p e r c h l o r a t e s .
T h e se sa m e a u th o rs (7,2 7) re p o rte d tr a n s itio n m e ta l c o m p le x e s o f
iro n (II) to z in c (II) a s w e ll a s c ad m iu m , m e rc u ry , an d s ilv e r w ith dmNN.
T h e ir a n h y d ro u s c o m p le x e s h ad s to ic h io m e try M (dm N N )3( C lO ^ g e x c e p t
fo r m e rc u ry an d s i l v e r , w h ic h w e re re p o rte d a s b is (dmNN) c o m p le x e s .
From th e in f r a r e d , u ltr a v io le t, an d v i s ib le s p e c tr a th e y a s s ig n e d
8
2+
o c ta h e d r a l g e o m e try to a l l th e ir tr is co m p o u n d s e x c e p t C u(dm N N )3 .
They d id n o t o b s e r v e a n y d - d tr a n s itio n fo r th e co p p er(II) c o m p le x .
The a b o v e a u th o rs (1,2) a ls o re p o rte d e ig h t- c o o r d in a te tr a n s itio n
m e ta l c o m p le x e s o f NN w ith m e ta l io n s m a n g a n e s e ( II), ir o n ( I I ) ,
c o b a lt ( I I ) , n ic k e l ( I I ) , c o p p e r ( I I ) , z in c ( I I ) , p a lla d iu m (II ), an d
c a d m iu m (II). All c o m p le x e s re p o rte d w e re a n h y d ro u s w ith s to ic h io m e try
M (N N )4 (C lO 4) 2 . T h e ir p o w d e r p h o to g ra p h d a ta sh o w e d th a t c o m p le x e s
o f m a n g a n e s e (II) to co p p er(II) w e re a ll iso m o rp h ic an d th a t th e cadm ium
an d z in c c o m p o u n d s w e re s im ila r . The s tru c tu re o f th e F e(N N )4(C lO 4) 2
c o m p le x h a s b e e n d e te rm in e d (3) by X -ra y d iffra c tio n m e th o d s . The
c o m p le x h a s a d is to r te d d o d e c a h e d ra l g e o m e try . The s tr u c tu r e is sh o w n
in F ig u re 3.
S tru c tu re o f te tr a k is ( l,8 - n a p h th y r id in e ) ir o n ( I I ) p e r c h lo r a te (3 ).
F ig u re 3
9
The ir o n - n itr o g e n d is ta n c e v a r ie s from 2.18 to 2.75 A. F our n itr o g e n s ,
o n e from e a c h n a p h th y rid in e m o le c u le , a re 2.18 to 2.25 8 d is ta n t from th e
iro n atom ; th e o th e r fo u r n itro g e n s a re a ll a t s ig n if ic a n tly g re a te r d i s ­
t a n c e s , 2.35 to 2 .7 5 X, in d ic a tin g v e ry u n s y m m e tric a l c o o rd in a tio n o f th e
n a p h th y r id in e s . C o o rd in a tio n o f th e n a p h th y rid in e m o fe c u le s th ro u g h
b o th n itro g e n s is in c o n tr a s t to th e m o n o d e n ta te ly c o o rd in a te d lig a n d in
CufN M lgClg re p o rte d by E nw all (21). T his r a i s e s a n u m b er o f im p o rta n t
an d in te r e s tin g q u e s tio n s a b o u t how th e c o o rd in a tio n s h o u ld be d e ­
s c r ib e d in th e s e tw o ty p e s o f c o m p le x e s . T h e se q u e s tio n s w ill re q u ire
fu rth e r s tu d y an d h a v e n o t b e e n d e a l t w ith in th is t h e s i s .
NITROGEN COMPLEXES OF C O P P E R (I):- In th e c o u rs e o f th is i n v e s ti g a tio n a n u m b er o f c o p p e r(l) co m p o u n d s w ere d is c o v e r e d w h ich
p ro v e d to h a v e u n u s u a l p r o p e r tie s ; th e lite r a tu r e on r e la te d com p o u n d s
i s su m m a riz e d h e r e .
C opper(I) c o m p le x e s w ith v a rio u s l i g a n d s , s u c h a s 1,10p h e n a n th r o lin e ( p h e n ) , .2,9- d i m e t h y l - 1,10 - p h e n a n th ro lin e (d m p ), 2,2' b ip y rid in e ( b ip y ) , d ia z o a m in o b e n z e n e , d ia z e n e an d s u b s titu te d
d ia z e n e s h a v e b e e n s tu d ie d ,(6,2 8 ,2 9 ). T h e se c o m p le x e s ' h a v e b e e n p r e ­
p a re d e ith e r b y re d u c tio n o f c o p p e r(Il) s a l t s o r by d ir e c t r e a c tio n o f
c o p p e r(I) s a l t s an d a n a p p ro p ria te b a s e . P re p a ra tio n a n d c h a r a c te r iz a ­
tio n o f s e v e r a l c o p p e r(l) c o m p le x e s o f m o n o s u b s titu te d d ia z e n e s
(RN=NH) h a v e b e e n re p o rte d (2 9 ). The c r y s ta l s tr u c tu r e s o f
(C H 3N =N C H 3)C u 2 C l2 a n d (C g H 5-N = N -N -C g H 5) 2 C u 2 h a v e b e e n
■
10
d e te rm in e d b y X-^ray d iffra c tio n m e th o d s (3 0 ,3 1 ).
The
(C H 3N =N C H 3)C u 2 C l2 m o le c u le c o n s i s t s o f in fin ite c h a in s o f c o p p e r a n d
c h lo rin e a to m s w ith c o p p e r ro u g h ly te tr a h e d r a lly c o o rd in a te d by th re e
c h lo rin e a to m s in th e c h a in an d by a n itro g e n lo n e p a ir from a d ia z e n e
m o le c u le (3 0 ). The (C g H 3 -N = N -N -C g H 3) 2 C u 2 m o le c u le e x is t s in a
d im e ric form in w h ic h th e d ia z o a m in o b e n z e n e m o le c u le s a re lin k e d by
n e a r ly lin e a r n itr d g e n - c o p p e r - n itr o g e n c o o rd in a tio n to fprm an e ig h tm em b ered rin g w ith a c o p p e r - c o p p e r d is ta n c e o f 2 .4 5 ^ (31).
R ed u c tio n o f 1 ,1 0 -p h e n a n th ro lin e , o r 2 ,2 '-b ip y r id in e c o m p le x e s o f
c o p p e r(Il) s a l t s in a m m o n ia c a l s o lu tio n w ith h y d r a z in e , so d iu m b i s u l ­
f i t e , o r h y d ro x y l a m ine h a s b e e n re p o rte d b y T a rta rin i (6 ). In som e
c a s e s th e c o p p er(I) c o m p le x e s w e re p re p a re d d ir e c tly from a m ix tu re o f
c o p p e r(l) s a l t an d th e lig a n d . The p re p a ra tio n o f C u (p h e n )2I , C u (M p y )I,
C u (P h e n )2 ClO^ a n d C u (M p y )2 ClO^ h a v e b e e n re p o rte d (6 ), T h e se co m ­
p le x e s w e re c o n d u c to rs in n itr o b e n z e n e s o lu tio n an d th e ir s p e c tr o p h o to m e tric m e a s u re m e n ts sh o w e d th e p r e s e n c e o f th e com m on io n CuL2
(L = p h e n o r b ip y ) . T here w a s a ls o so m e e v id e n c e for a s m a ll am ount o f
th e b rid g e d d im e r o f 2,9- d im e th y l- 1 ,1 0 -p h e n a n th r o lin e (dmp) in e q u i­
lib riu m : ■
X
11
The fo llo w in g r e a c tio n h a s b e e n p ro p o s e d fo r th p p r e s e n c e o f io n ic
s p e c ie s in th e s o lu tio n o f th is com plex:
2 C u(dm p)C l
— > C utdm p)* + C l" + C uC l
“ l
The s o lu tio n s p e c tr a sh o w e d a b p o rp tip n m axim a a t 21700 cm , in d ic a ­
tiv e o f C utdm p)^ io n (6 ), P e tre d is e t a l . (29) h a v e a ls o o b s e rv e d
s im ila r io n ic s p e c ie s w ith co p p er(I) c o m p le x e s in th e s o lu tio n an d h a v e
is o la te d th e C u(M py)^ io n a s i t s te tra p h e n y lb o ra te s a l t .
AIMS OF THIS RESEARCH:
All p re v io u s s tu d ie s on tr a n s itio n m e ta l c o m p le x e s o f 1,10p h e n a n th r o lin e a n d 2 ,2 '-b ip y r id in e (F ig u re I) h a v e sh o w n th a t th e s e
lig a n d s c o o rd in a te th ro u g h th e ir tw o n itro g e n a to m s to th e c e n tr a l
m e ta l. The [C u (p h e n )2X]X a n d [C u (b ip y )2X]X co m pound (X= Cl o r Br)
w e re sh o w n to c o n ta in f iv e - c o o r d in a te d c o p p er(II) io n , w h e re th e m e ta l
h a s a trig o n a l p y ram id g e o m e try . W hen s a l t s o f a n io n s o th e r th a n
h a lid e s w e re u s e d , p e rc h lo ra te an d n itr a te fo r i n s t a n c e , th e lig a n d s
w e re s t i l l found to c h e la te in th e sa m e m a n n e r, By c o n t r a s t , th e re p o rt
o f th e s tr u c tu r e d e te rm in a tio n o f C u(N N )2 C l2 b y X -ra y d iff ra c tio n m e th ­
o d s sh o w e d th a t th e n a p h th y n d in e m o le c u le b e h a v e s d iff e r e n tly (21),
Both h a lo g e n s a re c o o rd in a te d to th e m e ta l an d th e n a p h th y rid in e s a re
c o o rd in a te d th ro u g h o n ly o n e o f th e n itr o g e n s . T h is w a s th e o n ly tr a n ed­
itio n m e ta l c o m p le x w ith 1 ,8 -n a p h th y rid in e re p o rte d u n til 1 9 6 8 . This
u n e x p e c te d p ro p e rty o f 1 ,8 -n a p h th y rid in e c o m p ared w ith
12
1 ,1 0 -p h e n a n th ro lin e a n d 2 ,2'- b ip y r id in e s tim u la te d i n t e r e s t in s tu d ie s on
tr a n s itio n m e ta l c o m p le x e s c o n ta in in g v a rio u s a n i o n s . It h a s b e en
p o in te d o u t (7) th a t in 1 ,8 -n a p h th y rid in e an d i t s 2 ,7 -d im e th y l d e riv a tiv e
th e e le c tr o n p a ir s a re e x te n d e d in a p a r a lle l m an n er an d s e p a r a te d by
a p p ro x im a te ly 2.2 A, w h e re a s in p h e n a n th ro lin e th e Icne n itro g e n p a irs
a re n o t p a r a lle l b u t s u b te n d a n a n g le o f a b o u t 85° a t 2.00 R from th e
m e ta l c e n te r . T his c h a r a c te r is tic o f th e n a p h th y rid in e m o le c u le , w h ic h
i s s im ila r to th a t o f c a r b o x y la te io n , r e s u lts in th e fo rm atio n o f p o ly ­
n u c le a r c o m p le x e s w ith su b n o rm a l m a g n e tic s u s c e p t i b i l i t i e s . Two s u c h
c o m p le x e s h a v e in d e e d b e e n p re p a re d d u rin g th is w o rk . C o m p le x e s o f
2 .7 - d im e th y l-1 ,8 - n a p h th y r id in e w e re o b ta in e d to s tu d y th e e f f e c t o f th e
tw o m e th y l g ro u p s on c o o rd in a tio n c h a r a c te r is tic s c o m p ared w ith th e
u n s u b s titu te d l i g a n d . I s o la tio n o f m e ta l p e rc h lo ra te c o m p le x e s w ith
1 .8 - n a p h th y rid in e from a q u e o u s s o lu tio n s w a s c a r rie d o u t .to d e te rm in e
th e e f f e c t o f w a te r o f h y d ra tio n on c o o rd in a tio n c h a r a c t e r i s t i c s o f th e
lig a n d co m p ared w ith a n h y d ro u s c o m p o u n d s re p o rte d in th e lite r a tu r e
( 1 ,2 ,3 ) . C o m p le x e s o f m e ta l s a l t s o f n i t r a t e , s u l f a t e , a n d a c e ta te io n s
w e re a ls o p re p a re d to d e te rm in e th e e f f e c t o f th e s e a n io n s on its c o ­
o rd in a tin g p o w e rs . F in a lly , four co p p er(I) c o m p le x e s o f
1 .8 - n a p h th y rid in e an d i t s 2 ,7 -d im e th y l-1 ,8 -n a p h th y rid in e w e re is o la te d
in o rd e r to in v e s t ig a te th e n a tu re o f a n in c o r r e c tly re p o rte d c o m p le x in
th e lite r a tu r e (7 ).
EXPERIMENTAL
ANALYTICAL TECHNIQUES
The lig a n d 1 ,8 -n a p h th y rid in e a n d i t s 2 ,7 -d im e th y l d e riv a tiv e w e re
p re p a re d by u s in g th e P a u d le r a n d K ress p ro c e d u re s (2 1 ,2 2 ).
R e a g e n t g ra d e c h e m ic a ls w e re u s e d for a ll s y n th e s e s w ith o u t
fu rth e r p u r if ic a tio n .
The c o p p er(II) c o n c e n tr a tio n s w e re d e te rm in e d by a t i trim e tric
m eth o d u s in g EDTA s ta n d a r d s o lu tio n (0.01-0.02 M) an d f a s t S u lp h o n e
B lack F a s e n d - p o in t in d ic a to r (3 2 ). In som e c a s e s w h e re th e e n d -p o in t
w a s n o t s h a rp th e io d o m e tric m eth o d (33), u s in g s ta n d a r d so d iu m th io ­
s u lf a te s o lu tio n (0.1 N), w a s a p p lie d .
C opper(I) c o n c e n tr a tio n s w e re d e te rm in e d b y io d o m e tric titr a tio n
(33) o f a n a q u e o u s s o lu tio n o f th e c o m p le x w h ic h h a d b e e n p re v io u s ly
a ir o x i d iz e d .
M a n g a n e se (II) an d z in c(II) c o n c e n tr a tio n s w e re e s tim a te d w ith
s ta n d a rd EDTA s o lu tio n u s in g E riochrom e B lack T a s th e e n d - p o in t
in d ic a to r (3 2 ).
C o b a lt(II) c o n c e n tr a tio n s w e re d e te rm in e d by EDTA titr a tio n w h ic h
w a s p r e v io u s ly u s e d in th is la b o ra to ry (3 4 ).
N ic k e l(II) w a s d e te rm in e d b y g ra v im e tric m eth o d u s in g d im e th y lg ly o xim e a s p r e c ip ita n t (3 2 ).
S ilv er(I) c o n c e n tr a tio n s w ere d e te rm in e d by g ra v im e tric p ro c e d u re
an d p r e c ip ita te s w e re w e ig h e d o u t a s s ilv e r(I) c h lo rid e (3 3 ).
14
Anion c o n c e n tr a tio n s in th e c o m p le x e s w ere d e te rm in e d by an
a n io n e x c h a n g e m e th o d . A p y re x g l a s s co lu m n w h ic h w a s m ade in th is
la b o ra to ry w a s u s e d in th is e s tim a tio n . The s h a p e an d th e m e a s u re ­
m e n ts o f th is colum n a re show n in F ig u re 4 . The co lu m n w a s fille d up
to 15 cm w ith c a tio n e x c h a n g e r e s i n , D ow ex 50W -X 8, an d w a s re g e n e r­
a te d w ith 6 M h y d ro c h lo ric a c id . In c a s e o f co m p o u n d s c o n ta in in g
s i l v e r , th e colum n w a s r e g e n e ra te d w ith 6 M n itr ic a c id . The colum n
w a s w a s h e d w ith d i s t i l l e d w a te r s e v e r a l tim e s ; a b o u t 15-25 mg o f th e
sa m p le w a s w e ig h e d e x a c tly , th e n w a s d is s o lv e d in 10 ml o f w a te r o r an
o rg a n ic s o lv e n t an d w a s e lu te d th ro u g h th e c o lu m n . A fter w a sh in g th e
12 cm
11
12 cm
v
S c h e m a tic d ia g ra m o f th e io n - e x c h a n g e c o lu m n .
F ig u re 4
15
colum n w ith w a te r th re e t i m e s , th e e lu te d s o lu tio n s w e re c o lle c te d an d
titr a te d w ith s ta n d a rd 0.05 M so d iu m h y d ro x id e to p h e n o lp h th a le in end
p o in t. F ig u re 4 sh o w s th e s c h e m a tic d ia g ra m o f th e co lu m n b e in g u s e d
in th is e x p e rim e n t.
T o tal c a rb o n -h y d ro g e n a n a ly s e s w e re perfo rm ed b y C h e m a ly tic s
I n c ., T e m p e , A riz o n a .
C o n d u c ta n c e m e a s u re m e n ts w e re o b ta in e d in m e th a n o l o r nitrorm e th a n e s o lu tio n s o f th e c o m p le x e s u s in g a n In d u s tria l In s tru m e n ts
M o d el R C -1 6B2 c o n d u c ta n c e b rid g e . The c e ll w a s c a lib r a te d w ith a
s ta n d a rd p o ta s s iu m c h lo rid e s o lu tio n p re p a re d w ith c o n d u c ta n c e w a te r .
The in fra re d s p e c tr a (4 0 0 0 -2 5 0 cm "*■) w e re o b ta in e d w ith a Beckm an
In fra re d S p e c tro p h o to m e te r d o u b le -b e a m M o d el IR -2 0 in p o ta s s iu m b ro ­
m ide p e l l e t s . All s p e c tr a w e re c a lib r a te d w ith p o ly s ty re n e film .
D iffu s e r e f le c ta n c e s p e c tr a (3 6 0 -8 0 0 nm) o f th e c o m p le x e s w ere
o b ta in e d w ith a C ary M o d el 1411 D iffu se R e fle c ta n c e by u s in g Type I
illu m in a tio n w ith in te g r a tin g s p h e re a tta c h m e n t a t W a s h in g to n S ta te
U n iv e r s ity , P u llm a n , W a s h in g to n .
All th e e le c tr o n ic a b s o r p tio n s p e c tr a w e re m e a s u re d in m e th an o l
o r a c e to n itr ile s o lu tio n s o f th e c o m p o u n d s in m a tc h e d 10-m m or 1-mm
q u a rtz c e l l s u s in g a C ary -1 4 re c o rd in g s p e c tro p h o to m e te r.
M a g n e tic s u s c e p t i b i l i t i e s w e re m e a s u re d b y th e G ouy m ethod
u s in g a M e ttle r a n a ly t ic a l b a la n c e , H a rv e y -W e lls L-44V e le c tro m a g n e t
a n d a M ag n io n M o d el N o . HS425 p o w e r s u p p ly . All s u s c e p t i b i l i t i e s
16
w e re d e te rm in e d a t room te m p e ra tu re e x c e p t th o s e o f C u(N N )C l^ and
Cu(NN)Brg w h ic h w e re d e te rm in e d a t 196, 213.5, 250, 296, a n d 313°K.
Four d iff e r e n t fie ld s tr e n g th s w e re u s e d in e a c h s tu d y . The m e a s u re ­
m e n ts a t g a c h f ie ld w e re run in, tr i p lic a te an d th e a v e r a g e o f th e
!m easurem ents w a s o b ta in e d . The d a ta w e re u s e d to c a lc u la te th e gram
s u s c e p t i b i l i t i e s from th e e q u a tio n :
W h ere:
2 g . Aw
9
d .A .H 2
g = a c c e le r a tio n o f g ra v ity
Aw = w e ig h t c h a n g e
d = s a m p le d e n s ity
A = c r o s s - s e c t i o n a l a re a o f G ouy tu b e
H = m a g n e tic fie ld s tre n g th
M a g n e tic m om ents w e re o b ta in e d from th e e q u a tio n :
Ueff. = 2' 84 <XM • 1 ^ 2
W h ere: .
= m a g n e tic m om ent e x p r e s s e d in Bohr m a g n e to n
^M
"
Xg tim e s sa m p le m o le c u la r w e ig h t
T = d e g re e s K elv in .
The m a g n e tic fie ld w a s d e te rm in e d a s d e s c r ib e d by E n w all (21). D ia ­
m a g n e tic c o rre c tio n s w e re c a lc u la te d from th e v a lu e s g iv e n by F ig g is
a n d L ew is (3 5 ).
X -ra y p o w d e r d iff ra c tio n d a ta w e re o b ta in e d u s in g CuK^ ra d ia tio n
w ith th e s a m p le s c o n ta in e d in 0.03-0.05 mm c a p illa r y g l a s s tu b e s w h ic h
17
w e re m o u n ted in a c a m e ra w ith a d ia m e te r o f 57.3 mm on a P h illip s
E le c tro n ic s I n c . p o w e r s u p p ly . X -ra y s in g le c r y s ta l d a ta w e re c o lle c te d
by th e W e is s e n b e rg m eth o d u s in g CuK^ r a d i a t i o n .
18
PREPARATION OF COM POUNDS
I.
HALIDE COMPLEXES:
C u(N N )C Ig a n d Cu(NN)Brg: — A s o lu tio n o f 0.5 mmol o f CuXg
(X= C l o r Br) in 40 ml o f 95% e th a n o l w a s h e a te d to a b o u t 7 0 °C and
0.05 mmol o f NN w a s a d d e d . The s o lu tio n w a s a llo w e d to c o o l s lo w ly
u n til p r e c ip ita tio n w a s c o m p le te d . The o liv e - g r e e n C u(N N )C lg an d th e
brow n Cu(NN)Brg w e re c o lle c te d b y f il tr a tio n , w a s h e d w ith a few m illi­
l i t e r s o f 95% e th a n o l, a n d a ir d rie d . The co m p o u n d s w e re k e p t o v e r
c a lc iu m c h lo rid e o v e rn ig h t an d w e re u s e d w ith o u t a n y fu rth e r p u r if ic a ­
tio n .
C o (N N )g C lg :— To a s o lu tio n o f 0.238 g (Im m o l) o f C oC lg ' 6 HgO
in 30 ml o f a b s o lu te m e th a n o l 0.26 g (2 mmol) o f NN in 10 ml o f a b s o lu te
m e th a n o l w a s a d d e d . T his b lu e s o lu tio n w a s k e p t in a c lo s e d c h am b e r
to a v o id a n y p o s s i b i l i t y o f w a te r b e in g a b s o rb e d from th e a tm o s p h e re .
The b lu e c r y s ta ls w h ic h form ed u p o n s ta n d in g a t room te m p e ra tu re w e re
f i l t e r e d , w a s h e d w ith a b s o lu te e t h a n o l , a n d d rie d in a d e s ic c a to r o v e r
c a lc iu m c h lo r id e . F u rth e r p u r if ic a tio n w a s p erfo rm ed from a b s o lu te
m e th a n o l by th e sa m e p r o c e d u r e .
C u(dm N N )gC lg a n d C u(dm N N )gB rg:— S o lu tio n s o f I mmol o f
C uC lg ' 2 HgO o r CuBrg in 30 ml o f w a te r w e re m ixed w ith 0.316 g (2 mmol)
o f dmNN in 10 ml o f a b s o lu te m e th a n o l. The g ra y -b lu e C u(dm N N )gC lg
p r e c ip ita te an d o liv e - g r e e n Cu(dmNN)gBrg c r y s ta ls w e re c o lle c te d b y
f i l tr a tio n , w a s h e d w ith a b s o lu te m e th a n o l, an d a ir d r ie d . Both
19
c o m p o u n d s w ere r e c r y s t a lli z e d from a b s o lu te m e th a n o l an d w e re fin a lly
d rie d o v e r c a lc iu m c h lo r id e .
T ab le II
HALIDE COM POUNDS
O/ n=,!
\
C o lo r
C u (N N )C l2
36.31
2.29
24.01
26.80
36.34 2.18 23.91
C u(N N )B r2
27.18
1.71
17.97
45.21
27.78
1.68
17.84 45.18
Brown
C u(N N )2 C l2^
48.68
3.06
16.09
17.9 6
48.69
2.77
15.90
G reen
5Ie
C u(N N )2 Br2^
39.73
2.50
13.14
33.04
39.78
2.63
13.36 33.42
O ran g e
OO
LO
M
A
C oncn.
H
9.26
15.11
18.17
11.80
C
H
a ( molar)
C
Ma ’
Ab
t
CO
»
r
C onduc­
tiv ity
cm^ mho
Mx l O
52.40
4.14
14.35
—
Blue
C u(dm N N )2 Br2
44.50
3.73
11.77
29.61
44.19
3.57
11.66
—
O liv e g re e n
C u (p y )2 C l2
fo r c o m p a riso n
O
H -
CD
15.73
O
14.09
50
CD
4.47
cr>
53.28
12.16
10.64
O
C u(dm N N )2 C l2
15.19
CD
17.94 Blue
O s
18.13
CD
15.04
CO
O
C o(N N )2 C l2
26.61 O liv e g re e n
8.56
6.34
18.6
a M = m e ta l. ^ A= a n io n . c The c o n d u c tiv itie s w e re o b ta in e d in a b s o lu te m e th a n o l s o lu tio n s .
c^W ere f i r s t s y n th e s iz e d by E nw all (21). e The c o n d u c tiv itie s w e re o b ta in e d in DMF s o lu tio n s
21
2 . PERCHLORATE COMPLEXES;
. Cu(NN)^C0 1 0 4 ) 2 ' 4 H g O : - A queous s o lu tio n s o f 0.37 g ( I mmol) o f
c u p ric p e rc h lo ra te h e x a h y d ra te a n d 0.52 g (4 mmol) o f NN in 2 0 ml o f
w a te r w e re m ixed a n d the. b lu e p r e c ip ita te w a s c o lle c te d in a s in te re d
g la s s f u n n e l. The b lu e s u b s ta n c e w a s d rie d an d th e n r e c r y s ta lliz e d
from a m ix tu re o f a c e to n e an d a b s o lu te m e th a n o l (1 :1 ). W h en th is com ­
p o u n d w a s r e c r y s t a lli z e d from w a te r - a c e to n e m ix tu re (1:1) a b lu e
h y d ra te d c r y s ta llin e com pound w a s o b ta in e d . U pon le a v in g th e s e c r y s ­
t a l s a t room te m p e ra tu re fo r s e v e r a l m in u te s a b lu e p o w d e r w a s
o b ta in e d . The a n a ly s e s o f th is a n h y d ro u s com pound a lo n g w ith h y d ra te d
c r y s ta ls a re g iv e n in T a b le III. S in c e th e h y d ra te d c o m p le x w a s n o t
s ta b le th e c a rb o n -h y d ro g e n a n a ly s is w a s n o t p o s s ib le .
The w e ig h t l o s s
in th e com pound w h ic h w a s d e te rm in e d b y w e ig h in g t h e 'c r y s t a l s b e fo re
a n d a f te r th e d e c o m p o s itio n w a s c o n s i s t e n t w ith th e s e d e te r m in a tio n s .
M n(NN)4 (C lO 4) 2 * 4 H 2O , Co(NN)4(C IO 4) 2 ' 4 H3O ,
N i(N N )4(C lO 4) 2 • 4 H2O , an d Zn(NN)4 (C lO 4) 2: -
S o lu tio n s o f I mmol o f
-M (C lO 4) 2 • x H2O (M = M n , C o , N i, an d Zn) in 10 ml o f w a te r an d 4 mmol
o f NN in 5 ml o f w a te r w e re m ix ed in a s m a ll P e tri d is h . The s o lu tio n s
w e re k e p t a t room te m p e ra tu re p a r tia lly c o v e re d u n til th e c r y s ta ll iz a tio n
w a s c o m p le te d . The w e ll-fo rm e d c r y s ta ls w e re c o lle c te d in a s in te re d
g l a s s fu n n e l a n d a ir d r ie d . The co m p o u n d s w e re r e c r y s t a lli z e d from
th e ir a q u e o u s s o lu tio n s b y s im ila r p ro c e d u re an d w e re a n a ly z e d im m e­
d ia te ly a f te r i s o l a t i o n . T h e se h y d ra te d co m p o u n d s w e re n o t s ta b le in
22
a i r , th e l o s s o f th e w a te r o f h y d ra tio n w a s o b s e rv e d g ra d u a lly e v e n a t
room te m p e r a tu r e .
Zn(N N )2 ( C l C ) ^ ' 4 H2O : - To a s o lu tio n o f 0.2 64 g (Im m o l) o f
z in c (Il) p e rc h lo ra te h e x a h y d ra te in 5 ml o f w a te r 0,2 6 g (2 mmol) o f NN
w a s a d d e d an d k e p t in a c h a m b e r c o n ta in in g a b s o lu te m e th a n o l. W h ite
la th -fo rm c r y s ta ls w e re o b ta in e d u p o n d iffu s io n w h ic h w e re c o lle c te d
m a n u a lly on a f il te r p a p e r a n d d rie d o v e r c a lc iu m c h lo r id e .
Ag(NN)ClO^: — A s o lu tio n o f 0.13 g ( I mmol) o f NN in 10 ml o f warm
w a te r w a s a d d e d to a h o t
s o lu tio n o f 0.207 g (I mmol) o f s ilv e r(l) p e r ­
c h lo ra te in 50 ml o f w a te r . The s o lu tio n w a s a llo w e d to c o o l slo w ly
u n til th e c r y s ta ll iz a tio n w a s c o m p le te d . The n e e d le -fo rm c r y s ta ls w e re
c o l l e c t e d , w a s h e d w ith w a te r fo llo w e d b y a c e to n e , a n d d rie d o v e r
c a lc iu m c h lo r id e . The c o m p le x w a s r e c r y s t a lli z e d from h o t w a te r an d
d rie d a s a b o v e .
T a b le III
PERCHLORATE COMPOUNDS
i
/0
C
O a lC Q •
H
Ma
X
Ab -
/
/0
C
\
I o u riQ
H
M
C onduct iv ity
C o lo r
A
A (m olar)
C oncn.
cm^ mho M x lO 4
M n(NN)4 (ClO4) 2 ' 41iZ0
6.49 23.50
6.41 23.60 Y ellow
T9 7C
8.36
Co(NN)4(C lO 4) 2 ' 4 ^ 0
6.23 23.38
6.29 23.15 Pink
2 07d
2.70
6.78 23.28 B lu eg re e n
181d
. 5.83
7.51 23.12 Blue
2 14d
3.23
208°
7.14
N i(N N )4 C lO 4) 2 • 4 H9O
45.20. 3.79
6.90 23.39
Cu(NN)4(C lO 4) 2 " 4H 2 °
■7.43 23.26
Zn(N N )2(C lO 4) 2 - 4 K2O
32.21 3.38 10.96 33.34
Co(NN)4(C lO 4) 2
Cu(NN)4 (C lO 4) 2
Zn(NN)4(C lO 4),
44.66 3.55
32.12 3.05 11.18 33.72 W h ite
e
49.38 3.11
7.57 25.55
49.37 2.92
7.53 25.79 Pink
198°
8.92
e
49.08 3.09
8.11 25.40
48.79 2.82
8.18 25.60 Blue
206°
5.13
8.33 25.34
8.30 25.27 W h ite
203°
4.28
31.9 6 29.47
31.75 29.51 W h ite
102d .
2.14
e
Ag(NN)ClO4
a M = m e ta l. ^ A.= a n io n .
c
The c o n d u c tiv itie s w e re o b ta in e d in n itro m e th a n e s o lu tio n s .
c o n d u c tiv itie s w e re o b ta in e d in a b s o lu te m e th a n o l s o lu tio n s . e P re v io u s ly re p o rte d ( I ) .
d
The
24
3,
NITRATE COMPLEXES:
Co(NN)4 (N O 3) 2 * 6 H2 O , N i(N N )3 (N O 3)2 * 4 H3 O , a n d
Zn(NN)4 (N O 3) 3 ' 6 H3O: — S o lu tio n s o f I mmol o f M (N O 3) 3 ' 6 H3O
(M = C o , N i , o r Zn) in 10 ml o f w a te r a n d 0.521 g (4 mmol) o f NN in 5 ml o f
w a te r w e re m ixed a n d k e p t in a p a r tia lly o p e n P e tri d is h a t room te m p e r­
a tu re u n til th e c r y s ta ll iz a tio n w a s c o m p le te d . The c r y s t a l s w e re
c o l l e c t e d , w a s h e d w ith 95% e th a n o l an d d rie d o v e r c a lc iu m c h lo rid e in
a d e s i c c a t o r . The c o m p o u n d s w e re r e c r y s t a lli z e d from th e ir a q u e o u s
s o lu tio n s by a s im ila r p r o c e d u r e . ' T h e se co m p o u n d s w e re n o t s ta b le a t
room te m p e r a tu r e , th e w a te r o f h y d ra tio n b e in g l o s t upon s ta n d in g in a ir
o r o v e r c a lc iu m c h lo rid e .
M n(N N )3 (N O 3) 3: — C o m m e rc ia lly a v a ila b le 50% m a n g a n e s e
n itr a te s o lu tio n , 5 m l, w a s m ixed w ith 0.26 g (2 mmol) o f NN in a P e tri
d is h a n d w a s k e p t c o v e re d in a d a rk p la c e for a b o u t o n e w e e k . The
y e llo w w e ll-fo rm e d c r y s ta ls w e re s e p a r a te d m a n u a lly o n a f il te r p a p e r
an d w e re w a s h e d w ith c h lo ro fo rm . The c r y s ta ls w ere k e p t in a c lo s e d
v ia l c o v e re d w ith b la c k p a p e r to p r o te c t th e c r y s ta ls from d e c o m p o s i­
t i o n , a n d k e p t in a d e s ic c a to r . T his co m p o u n d w a s h y g ro s c o p ic and
lig h t s e n s i t i v e . W hen s o lu tio n o f th e com pound w a s e x p o s e d to th e
lig h t a b la c k p r e c i p i t a t e , n o t v e ry s o lu b le in in o rg a n ic a c i d s , w a s o b ­
t a in e d . N o id e n tif ic a tio n o f th is b la c k s u b s ta n c e w a s m a d e .
C u(N N )2 ^g(N O 3) 3 a n d C u(N N )2 (N O 3) 2: -
S o lu tio n s o f 0.296 g
(I mmol) o f c u p ric n itr a te h e x a h y d ra te in 10 ml o f w a te r an d 0.39 g
25
(3 mmol) o f N N in 5 ml o f w a te r w e re m ix e d a n d k e p t in a p a r t i a l l y c o v ­
e re d P e tri d i s h .
U pon s lo w e v a p o r a tio n o f th e s o lu tio n a t room te m p e r ­
a tu r e , b lu e c r y s t a l s w e re i s o l a t e d a f t e r a few d a y s . The c r y s t a l s w e re
c o l l e c t e d b y f i l t r a t i o n , w a s h e d w ith a s m a ll v o lu m e o f c h lo ro fo r m , a n d
a i r d r i e d . F u rth e r r e c r y s t a l l i z a t i o n o f th e co m pound from i t s a q u e o u s
s o lu tio n w a s c a r r ie d o u t b y th e s a m e m e th o d . The co m pound w a s d rie d
o v e r c a lc iu m c h lo r id e a n d a n a l y z e d a s CufNNOg ^ ^ (N O g )^ . W h en 0.2 g
o f t h i s c o m p le x w a s d i s s o l v e d in 30 ml o f a b s o l u t e m e th a n o l c o n ta in in g
10 ml o f 2,2 1- d im e th o x y p r o p a n e a n d w a s re flu x e d for 8 h o u rs a b lu e s u b ­
s t a n c e w a s o b t a i n e d . T h is co m pound w a s c o l l e c t e d by f i l t r a t i o n ,
w a s h e d w ith c h lo ro fo rm , a n d d rie d o v e r c a lc iu m c h l o r i d e , The s t o i ­
c h io m e try o f th e c o m p le x w a s p ro v e d b y i t s e le m e n ta l a n a l y s e s a s
C u (N N ^ (N C )3) 2 . T his l a t t e r b is c o m p le x w a s a l s o p r e p a r e d by d i s s o l v ­
in g a n a p p r o p r ia te r a tio o f th e c u p r ic n i t r a t e a n d NN in d ry m e th a n o l by
a s i m i l a r m e th o d .
C o (N N )2 (N O 3) 2 =— A s o lu tio n o f 0.291 g ( I mmol) o f co b alt(II)
n i t r a t e h e x a h y d r a te in 10 ml o f a b s o l u t e e th a n o l w a s m ix ed w ith 0.26 g
(2 mmol) o f NN in a 2 5 -m l b e a k e r . T his s o lu tio n w a s k e p t in a c lo s e d
c h a m b e r for a fe w d a y s u n til th e p in k c r y s t a l s w ere i s o l a t e d . The c r y s ­
t a l s w e re c o l l e c t e d m a n u a lly on a f i l t e r p a p e r a n d d rie d o v e r c a lc iu m
c h l o r i d e . T his a n h y d ro u s s u b s t a n c e w a s n o t s t a b l e a n d i t a b so rb e d
w a te r from th e a tm o s p h e r e upon s ta n d i n g in a i r . The r e p r o d u c ib ility o f
t h i s b is co m pound w a s p o o r a n d m o s t o f th e tim e i t w a s i s o l a t e d w ith
26
d if f e r e n t n u m b e rs o f h y d ra tio n w a te r „ The h y d ra tio n n u m b e r v a r ie d w ith
th e s o l v e n t im p u rity § s w e ll a s th e p e rio d o f tim e it w a s k e p t in s o l u ­
tio n d u rin g th e c r y s t a l l i z a t i o n .
Ag(NN)NO3: — A s o lu tio n o f 0.17 g (Im m o l) o f AgNO3 in 50 ml o f
w a t e r w a s m ix ed w ith 0.13 g ( I mmol) o f NN in 10 ml o f w a t e r . The w h ite
p r e c i p i t a t e w a s c o l l e c t e d b y f i l t r a t i o n , w a s h e d w ith a c e t o n e , and a ir
d r ie d . This w h ite s u b s t a n c e w a s d i s s o l v e d in a s u f f i c i e n t am o u n t o f h o t
w a t e r a n d a llo w e d to c o o l s lo w ly . The w h ite n e e d l e s w e re c o l l e c t e d on
a s i n t e r e d g l a s s fu n n e l a n d w a s h e d w ith a fe w m i l l i l i t e r s o f 95%
e t h a n o l . The c r y s t a l s w e re a i r d rie d a n d k e p t in a d e s i c c a t o r o v e r
c a lc iu m c h lo r id e .
T ab le IV
NITRATE COMPOUNDS
% C a l c d .-
/
C
N
Ma
% Found
\ (
Ab
C onducLXVityw
C
H
M
C o lo r
A
A (molar)
C oncn.
cm^ mho M x lO 4
M n(N N )2(N O 3) 2
12.51 28.23
12.77 28.09 Y ellow
182
6.33
C o (N N )2(N O 3) 2
13.30 27.98
13.08 2 7.81 Pink
187
14.32
42.91 2.70 14.19 27.68
42.99 2.62 14.34 2 7.99 Blue
152
13.17
44.35 2.79 13.53 26.40
43.96 2.76 13.64 26.52 Blue
136
12.22
37.31 3.91 11.40 24.08
37.64 3.56 11.31 23.92 B lu e g re e n
185
8.97
C u( n n ) 2 n o 3) 2
C u(N N ) 2 16(N O ;
1^2
N i(N N )2 (N O 3) 2 4 H 20
Co(NN)4 (N O 3) 2 GH2O 47.35 4.47
7.26 15.2 8 47.34 4.43
7.58 15.57 Pink
208
7.14
46.98 4.44
7.99 15.16 47.33 4.2 5
8.22 15.39 W h ite
174
11.56
35.72 20.88 W h ite
30
21.73
Zn(NN)4 (N O 3) 2 *GH2O
Ag(NN)NO3
a M = m e t a l . ^ ^L- a n i o n .
so lu tio n s.
35.95 20.67
All th e c o n d u c t i v i t i e s w e re o b ta in e d in a b s o l u t e m e th a n o l
28
4.
COPPER(I) COMPLEXES:
C u ^(N N )C lg a n d CugW m NN )ClgZ-T To a s o lu tip n o f 0.198 g
( I mmol) o f C uC l in 40 ml o f warm a c e t o n i t r i l e 0.065 g (0.5 mmol) o f NN or
0.079 g (0.5 mmol) o f dmNN in 10 ml o f a c e t o n i t r i l e w a s a d d e d . The
o ra n g e p r e c i p i t a t e w a s c o l l e c t e d b y f i l t r a t i o n , w a s h e d w ith a b s o lu t e
■m e t h a n o l , a n d a i r d r i e d . T h e s e c o m p o u n d s w e re p o t s o lu b le in m o st
o rd in a ry o r g a n ic s o l v e n t s . A queous s o lu tio n s , o f t h e s e c o m p o u n d s w e re
u n s t a b l e in a i r a n d th e co p p er(I) w a s a i r o x id iz e d to a g re e n copper(II)
sp ec ie s.
The p r e p a r a t io n o f t h e s e c o m p le x e s u n d e r n itr o g e n a tm o s p h e re
g a v e p u re p r o d u c ts w h ic h w e re u s e d w ith o u t a n y fu rth e r p u r if ic a tio n .
Cu(NN)ClO^z— To a s o lu tio n o f 0.1 g o f Cu(NN)^(C10^)g , in 30 ml
o f a b s o l u t e m e th a n o l, 10 ml o f 2,21- d im e th o x y p r o p a n e w a s a d d e d . This
s o lu tio n w a s r e flu x e d for four h o u rs a n d 0.3 g o f c u p ric p e r c h lo r a te
h e x a h y d r a te w a s a d d e d . After re flu x in g t h i s s o lu tio n for 12 ho u rs i t w a s
c o n c e n t r a t e d w ith w arm in g u n d e r r e d u c e d p r e s s u r e to o n e - h a l f th e v o l ­
ume a n d k e p t u n d e r n itr o g e n in a c h a m b e r c o n ta in in g a b e a k e r o f so d iu m
h y d ro x id e p e l l e t s . The o ra n g e c r y s t a l s w e re c o l l e c t e d by f il tr a tio n ,
w a s h e d w ith c h lo ro fo r m , a n d d rie d o v e r c a lc iu m C h lo rid e . The com ­
p o u n d w a s r e c r y s t a l l i z e d from nitromethane s o lu tio n b y a s im ila r m e th o d .
C p(dm N N )2 ClO4Z -
A s o lu tio n o f 0.14 g (0.42 mmol) o f c p p ric p e r ­
c h lo r a te h e x a h y d r a te in 40 ml o f a b s o l u t e p ie th a n o l a p d IO ml o f 2 ,2 'd im e th o x y p ro p a n e w a s r e f lu x e d for s i x h o u rs fo llo w e d b y th e a d d itio n o f
0.158 g (I mmol) o f dm N N . After re flp x in g for 18 h o u rs t h e li g h t brown
29
s o l u t i o n w a s a llo w e d to c o o l s lo w ly . The brow n n e e d l e s w e re c o l l e c t e d
b y f il tr a tio n and. w e re r e c r y s t a l l i z e d from a b s o l u t e m e th a n o l o r n i t r o m e t h a n e . The p ro d u c t w a s w a s h e d w ith chloroform a n d d r ie d o v e r
c a lc iu m c h lo rid e .
T ab le V
COPPER(I) COM POUNDS
/----------% C a l c d . - C
H
Ma
% Round
r
AD
C onductiv ity
C
H
M
C o lo r
A
A(molar)
C oncn.
Cm^ mho M x l O 4
C u 2(N N )O l2
29.28 1.85 38.73
29.36 1.62 38.83
O ran g e - 132^
3.81
C u 2(d m N N )C l2
33.72 2.83 35.68
34.45 2.85 35.39
O ra n g e
122^
9.09
Cu(NN)ClO^
32.78 2.06 21.67
32.67 2.00 21.36
O ra n g e
I O ld
15.62
C u(dm N N )2 C104
50.10 4.2 0 13.25 28.74
50.20 4.25 12.98 20.69
Brown
112®
0.84
a M = m e t a l . ^ A = a n i o n . C,c*, e The c o n d u c t i v i t i e s w e re o b ta in e d in; a c e t o n i t r i l e ( c ) , n itr o m e th a n ( d ) , a n d a b s o l u t e m e th a n o l {e) s o l u t i o n s .
RESULTS AND DISCUSSION
PART I — HALIDE COMPLEXES:
The a n a l y t i c a l a n d p h y s i c a l d a ta for h a lid e c o m p le x e s a re r e ­
p o rte d in T ab le II . A ttem p ts to d e te r m in e th e m e ltin g p o in t o f th e
c o m p le x e s w e re u n s u c c e s s f u l due to d e c o m p o s itio n o f th e c o m p o u n d s a t
te m p e r a t u r e s o f a b o u t 2 4 0 ° C . The c o m p o u n d s a re a ll s t a b l e on e x p o s u r e
to l i g h t a n d a i r e x c e p t C u C d m N N ^ C l2 , w h ic h g r a d u a lly c h a n g e s from
b lu e to brow n u p o n s ta n d i n g in s u n lig h t for tw o w e e k s .
The m a g n e t ic s u s c e p t i b i l i t i e s o f a l l copper(II) c o m p le x e s w e re
d e te r m in e d a n d from th e o b s e r v e d s u s c e p t i b i l i t i e s t h e . m a g n e t i c m om ents
p e r c o p p e r atom w e re e v a l u a t e d . T h e -m a g n e tic m om ents o f a l l co m ­
p l e x e s (T able V I), a p a r t from m o n o - c o m p l e x e s , l i e in t h e ra n g e
1.99-2.01 B .M . The n o rm al m a g n e tic m om ent a s s o c i a t e d w ith copper(II)
c o m p o u n d s i s 1.8-2.2 B .M . (12). From th is i t i s c o n c lu d e d t h a t th e
co p p er(II) c o m p le x e s o f NN a n d dmNN w ith m a g n e tic m o m en ts o f 1.992.01 B .M . a re m o n o n u c le a r; on th e o th e r h a n d , th e C u (N N )C l2 a n d
Cu(NN)Br2 c o m p le x e s w ith room te m p e ra tu re m a g n e tic m o m en ts of
1.69 B .M . a n d 1.59 B .M . r e s p e c t i v e l y a re s im ila r to t h o s e o f copper(II)
c a r b o x y l a t e s (12). As n o te d in th e in t r o d u c t i o n , t h e s e l a t t e r co m pounds
e x h i b i t s u b n o rm a l m a g n e tic m o m e n t s , a n d h a v e a maximum in a p lo t o f
m o la r m a g n e tic s u s c e p t i b i l i t y v e r s u s t e m p e r a t u r e . The m a g n e tic s u s ­
c e p t i b i l i t i e s o f th e C u (N N )C l2 a n d Cu(NN)Br2 c o m p o u n d s w e re d e t e r ­
m in ed a t s e v e r a l d if f e r e n t te m p e r a t u r e s a n d it w a s found t h a t th e y w e re
32
T ab le VI
MAGNETIC SUSCEPTIBILITY OF DATA OF HALIDE COMPLEXES
D ia m a g n e tic
C orr.
C o rre c tio n
, n6
c . g . s . u . x 10
X m x106
c .g .s .u .
C u(N N )2 C l2
193
1704
296
2.01
C u (N N )2 Br2
217
1670
296
1.99
C o(N N )2 C l 2
193-
8149
298
4.40
C u(dm N N )2 Br2
2 63
1670
296
1.99
C u (N N )C l2
120 .
1107
326
1.70
1153
313
1.70
1201
297
1.69
1376
250
1.66
1497
213.5
1.60
1530
196
1.55
1081
326
1.68
1035
313
1.61
1066
296
1.59
1109
250
1.49
1163
312.5
1.41
1110
196
C om pound
Cu(NN)Br2
143
T , °K
^ e ff.
B .M .
1.32
33
te m p e ra tu re d e p e n d e n t a n d s im ila r to copper(II) a c e t a t e m o n o h y d ra te
(T able VI). In Fig u re 5 , p lo ts o f m o la r m a g n e tic s u s c e p t i b i l i t i e s v e r s u s
te m p e ra tu re a re s h o w n .
The Cu(NN)Br2 h a s a maximum a t a b o u t 2 15°K
a n d th e maximum for C u (N N )C l2 i s b e lo w 19 6°K . The
C u 2(CHgCOO)^ ' 2 H2O c u rv e is sh o w n for c o m p a r i s o n , w ith maximum a t
a b o u t 2 6 0°K. T h e s e d a ta s u g g e s t t h a t t h e s e tw o c o m p le x e s a re b rid g e d
b in u c le ar m o le c u le s .
- S in c e h a lid e b r id g e d copper(II) c o m p o u n d s are v e r y c o m m o n , a n d
t h i s su b n o rm a l m a g n e t ic b e h a v io r w a s o b s e r v e d o n ly in h a l i d e co m ­
p l e x e s i t is p o s s i b l e t h a t t h e s e m ig h t be h a lid e b rid g e d d im e r s . It h a s
b e e n r e p o r te d in th e l i t e r a t u r e t h a t copper(II) c o m p o u n d s c o n ta in in g
h a lid e b rid g e s do n o t e x h i b i t s u b n o rm a l m a g n e tic p r o p e r tie s , a t room
te m p e r a tu r e (3 6 ). Thus i t s e e m s l i k e l y t h a t 1 ,8 -n a p h th y rid in e m o le c u le s
a re b rid g e d a c r o s s th e tw o c o p p e r a to m s in C u (N N )C l2 a n d Cu(NN)Br2
com pounds.
M o le c u la r w e ig h ts w o u ld be u s e f u l on co n firm in g th e a b o v e
h y p o t h e s i s b u t th e s p a r in g s o l u b i l i t i e s o f th e copper(II) h a l i d e com ­
p o u n d s p r e v e n te d th e d e te r m in a tio n o f m o le c u la r w e i g h t s .
By c o m p a r is o n o f X -ra y p o w d e r p h o t o g r a p h s , i t w a s found t h a t th e
c r y s t a l s o f C u (N N )C l2 a n d Cu(NN)Br2 w e re is o m o rp h o u s w h ic h w ill be
d i s c u s s e d in th e fo llo w in g p a r a g r a p h s .
The c o m p a r is o n o f C u (N N )C l2 a n d Cu(NN)Br2 in f r a r e d s p e c t r a
s h o w e d t h a t b o th w e re s im i l a r in th e re g io n 4 0 0 0 -3 0 0 cm \
The lig a n d
34
x 10
iooo r
I C u 2(C H 3C O O )4 • 2 H2O
.
II C u ( C g H 6N 2)Bi2
III C u ( C fiH fiN 9) C l 9
F ig u re 5.
M a g n e tic s u s c e p t i b i l i t i e s o f t h e s u b n o rm a l C opper(II)
c o m p le x e s.
F ig u n e 6.
36
mode for 1,8- n a p h th y r id i n e h a v e b e e n a s s i g n e d a n d r e c o r d e d in the
ra n g e 1 7 0 0 -6 5 0 cm * by Armarego e t a h (37) „ As w o u ld b e e x p e c t e d , th e
lig a n d in fr a r e d s p e c tru m a l t e r e d on c o o r d in a tio n . In T a b le V II, th e
lig a n d m o d es w h ic h s h if t s i g n i f i c a n t l y u p o n c o o rd in a tio n a n d th e p a r e n t
lig a n d v ib r a tio n s a re l i s t e d .
P re v io u s s t u d i e s (38) on c o m p le x e s c o n ta in in g m e t a l - h a l o g e n
b o n d s i n d i c a t e t h a t th e m e t a l - c h l o r i n e s t r e t c h i n g f r e q u e n c i e s o c c u r b e tw e e n 3 5 0 -2 5 0 cm a n d m e ta l- b r o m in e f r e q u e n c i e s from b e lo w
-I
2 5 0 -2 0 0 cm . The b rid g e d c o p p e r - c h l o r i n e a n d te rm in a l c o p p e r - c h l o r i n e
s t r e t c h i n g v i b r a tio n s h a v e b e e n o b s e r v e d a t 311 cm
a n d 32 6 -3 3 0 cm
r e s p e c t i v e l y ( 3 9 ,4 0 ) . The te rm in a l c o p p e r - c h l o r i n e s t r e t c h i n g v i b r a ­
t io n s in C u fp y jg C lg a n d E t ^ N ^ C u C l ^ c o m p o u n d s h a v e b e e n re p o rte d a t
287 cm ^ a n d 2 6 8 -2 89 cm ^ r e s p e c t i v e l y ( 4 1 ,4 2 ) . In T a b le VIII, th e
c o p p e r - c h l o r i n e s t r e t c h i n g f r e q u e n c i e s for b rid g e d a n d te rm in a l c h lo rid e
i o n s , in som e copper(II) c o m p le x e s a re l i s t e d .
The te rm in a l c o p p e r -
c h lo r in e s t r e t c h i n g fr e q u e n c y in C u(N N )^C lg c o m p le x ( s e e Figure 8)
-I
o c c u r s a s a s in g le b ro a d b a n d w ith th e a b s o r p tio n maximum a t 282 cm
w h ic h i s in good a g r e e m e n t w ith th e v a l u e s re p o rte d for C u(Py)^C lg a n d
(E t^ N )g C u C l^ c o m p o u n d s . In Cu(N N )Clg th e s h a p e o f t h i s b a n d is q u ite
d if f e r e n t a n d s h i f t s to h ig h e r f r e q u e n c y ( s e e Figure 8) w h ic h i n d i c a t e s
d i f f e r e n t c o p p e r - c h l o r i n e b o n d (s) c o m p a re d w ith th e C u(N N )gC lg co m ­
p l e x c o n ta i n in g tw o te r m in a l c h lo r id e i o n s (Figure 2). The c o p p e r b ro m in e s t r e t c h i n g f r e q u e n c i e s w e re n o t o b s e r v e d in t h i s s tu d y w h ic h
T ab le VII
SELECTED INFRARED ABSORPTIONS (4 0 0 -2 50 CM X) OF HALIDE COMPLEXES*
Band
I
II
III
IV
V
VI
VII
VIII
IX
X
XI
XII
XIII
XIV
XV
XVI
XVII
XVIII
XIX
NN
1555
1492
1360
1288
•
•
•
vs
vs
w, s h
s
1128
1045
1026
9 69
953
835
809
773
760
600
402
1572
1510
1350
1240
•
»
vs
m
s
vs
vw
vs
vs
m ,s h
vs
w
m
300 v w
2 72 v w
Cu(NN)Br2
C u(N N )2 C l 2
s
vs
s
m
1570 m
1510 v s
1580 s
1495 v s
1570 s
1502 v s
*
*
s
m
vw
m
w
vw
s
m
vs
vw
m
1138
1082
1056
981
9 63
847
842
834
790
638
435
300
2 80
245
C u (N N )C l2
•
«
»
•
1138
1082
1055
' 982
9 65
848
842
830
790
640
437
1350 s
1240 w
300 s, br
290 m
245 s
#
#
*
#
*
1236 v s
ft
m
w.
vw
w
vw
s
s
m ,s h
vs
vw
vw
vw
vw 7s h
s
*
ft
ft
C
1136
1057
1031
■ 9 68
9 58
842
835
800
780
622
420
282
*
#
*
*
s
m
m
vw
vw
s 7s h
vs
vs
vs
m
m
v s , br
C u(N N )2Br2
*
»
C o(N N )2 Cl
1565 s
1502 v s
*
1240
1147
1128
1062
1035
970
9 60
m
m
s
s
m
vw
vw
845 s 7sh
840 v s
800 vs
785 v s
630 w
427 w
275 w, sh
2 65 w, sh
1234
1145
1128
1063
1035
970
957
m
s
s
s
m
vw
w '
840
835
803
785
627
426
vs
s 7sl
vs
vs
in
m
310 s
285 m
257 m
* The a s s i g n m e n t s a re : s, s tro n g ; v, v e ry ; m, medium; sh, s h o u ld e r; br, broad; w, w e a k
38
M ic ro n s
5.5
6
6.5
7
7.5
8
9
10
11
12
14
16
18
20
25
30
40
TRA N S/
5
2000
F ig u re 7.
In fra re d S p e c tra o f
a n d CgHgNg
39
T T "'I... I
C u I C vH ^ I C I .
:E N T T K A N S l
V— I"
I--I
C u I C 0H - N 0 I0 CI
‘j " ! " ) • • • " j
Fig u re 8 .
In frared S p e c tra o f C u (C g H g N 2) C l 2 a n d C u ( C g H gN 2) 2C l 2 .
40
T ab le VIII
INFRARED ABSORPTIONS OF SOME Cu(II) COMPLEXES a
|u, B. M .
C u - C l b, C M ” 1
C u(N N )2 C l 2
2.01
282
C u (N N )C l2
1.-69
300, 290
C(PyO) C u C l2 ] 2C
0.59-1.06, 0.63
3 3 0 ,3 1 1
[ ( S - C H 3P y O )C u C l2 ] 2
0.55, 0.97
320
[ ( 4 - C H 3P y O )C u C l2 ] 2 •
0.49, 0.52
327, 312
[(PyO)2 CuC l2 ] 2
0.46, 0.63
3 1 0 ,2 8 0
(2 - C H 3PyO) 2 C u C l2
1.95
328
( S - C H 3PyO)2 CuC l2
....
322
[ 2 , 6 - ( C H 3) 2 PyO J2 CuC l2
1.91
319, 297
C u 3 C l 6 [ 4 - C l ( q u i n O ) ] 2C
2.07
308, 290
C u C l2 ( 4 - C l - P y ) 2G
1.83
294^
C uC l2(Py)2
....
287
289 s h , 268
(Et4N )2 C u C l46
a
R e fe re n c e 3 9 .
b
C om m as s e p a r a t e m ore th a n o n e in fr a r e d b a n d .
C PyO = p y rid in e N - o x id e ; Q uinO = quinoline N -o x id e ; Py = p y r i d i n e .
^ R e f e r e n c e 4 2 . e R e fe re n c e 42.
41
i n d i c a t e s t h a t th e b a n d s o b s e r v e d a t 3 0 0 (s,b r) cm * a n d 290(m) cm- '1' are
c o p p e r - c h l o r i n e s t r e t c h i n g v ib r a tio n s o f Gu(NN)Clg c o m p le x .
The r e f l e c t a n c e s p e c t r a o f co p p er(II) h a lid e c o m p le x e s of
1 ,8 -n a p h th y rid in e a re sh o w n in Figure 9 a n d t h e i r a b s o r p tio n m axima a re
l i s t e d in T a b le IX. The d if f u s e r e f l e c t a n c e s p e c t r a o f C u(N N )C lg and
Cu(NN)Brg a re s i m i l a r w ith a b s o r p tio n m axim a a t 13240 cm ^ and
13160 cm- ^ r e s p e c t i v e l y w h ic h i s c o n s i s t e n t w ith th e w e a k e r lig a n d
fie ld s tr e n g th o f bro m id e c o m p a re d w ith c h l o r i d e .
From m a g n e tic s u s c e p t i b i l i t y m e a s u r e m e n t s . X -ra y p o w d e r p h o to ­
g rap h s,
a n d v i s i b l e a n d u n fra re d s p e c t r a o f Cu(NN)Xg (X= C l or Br)
th e r e a r e s e v e r a l p o s s i b l e s t r u c t u r e s w h ic h c a n be s u g g e s t e d for t h e s e
c o m p l e x e s . Among a l l p o s s i b l e s t r u c t u r e s th e r e i s o n ly o n e s tr u c tu r e
w h ic h f it s th e d a t a . In Fig u re 6-A , a d im e r m o le c u le o f Cu(NN)Xg is
sh o w n in w h ic h tw o n a p h th y rid in e m o le c u le s a re c o o r d in a te d th ro u g h
tw o n itr o g e n s a c r o s s th e tw o Cu(II) io n s w ith two h a lo g e n ato m s form­
in g b r id g e s in th e p la n e p e r p e n d i c u l a r to th e p la n e o f t h e n a p h th y rid in e
m o le c u le s a n d tw o te r m in a l h a lo g e n s o n e a c h s id e o f th e b in u c le a r
c o m p le x . T h e s e tw o te rm in a l h a lo g e n s m ay c o o rd in a te to th e n e ig h b o r ­
ing m o le c u le s u n s y m m e t r i c a l l y , g iv in g r i s e to one s h o r t a n d o n e long
c o p p er-ch lo rin e bond d is ta n c e .
Fig u re 6 -B s h o w s a n a l t e r n a t i v e p o s ­
s i b l e s tr u c tu r e in w h ic h c o p p e r a to m s a re b rid g e d in p a i r s b y two
n a p h th y r id in e m o l e c u l e s w ith th e fo u r h a lid e io n s o c c u p y in g te rm in a l
p o s i t i o n s . In F ig u re 6- B , b o th te r m in a l c h lo rid e io n s a re e q u iv a l e n t
42
---- C u (N N )C l2
—
Cu(NN)Br
----- C u(N N )2 Cl
-
C u(N N )9 Br,
\
RELATIVE INTENSITY
Il r \
-
12000
Fig u re 9 .
17000
25000 cm
D iffu se r e f l e c t a n c e o f h a lid e c o m p le x e s .
43
T a b le IX
VISIBLE ABSORPTION SPECTRA OF HALIDE COMPLEXES (CM™1)
C h arg e-tra n sfe r
a n d lig a n d b a n d s
d-d bands
C u (N N )C l2
2 6 8 0 0 , 21980 sh
14660 s h , 13240
Cu(NN)Br2
2 8 4 0 0 , 21740
14490 s h , 13160
C u (N N )2 C l 2
27030 s h
1 4 8 0 0 , 13330 sh
C u(N N )2 Br2
28170 s h , 22470 s h
13000
C o(N N )2 C l *
1 7 1 8 0 , 1 6 7 5 0 , 1 6 3 9 0 , 15950
* The s p e c tru m w a s o b ta in e d in n itr o m e th a n e s o lu tio n .
a n d th e c o p p e r - c h l o r i n e s t r e t c h i n g v ib r a t i o n s w o u ld a p p e a r a s a s in g le
b a n d , a s is o b s e r v e d in th e C u(N N )2 C l 2 s p e c tru m . The in fra re d v i b r a ­
tio n f r e q u e n c i e s o f c o p p e r - c h l o r i n e s t r e t c h i n g b a n d s in C u (N N )C l2
c o m p le x i n d i c a t e t h a t th e c h lo rid e io n s a re n o t e q u i v a l e n t a n d th e y
p r o b a b ly h a v e d if f e r e n t t y p e s o f c o o r d in a tio n to th e c o p p er(II) io n . This
i s in a g r e e m e n t w ith th e s tr u c tu r e 6-A w h ic h c o n ta i n s tw o d iff e r e n t
k in d s o f c h lo r in e s c o o r d in a te d to th e c o p p e r a to m . The s tr u c tu r e 6-B
c o n t a i n s o n ly o n e k in d o f c o p p e r - h a l o g e n b o n d , w h e r e a s th e in fra re d
s p e c tru m s e e m s to c a l l for tw o .
C u (N N )2 C l 2 a n d C u (N N )2 Br2: -
The m a g n e tic m o m e n ts o f t h e s e
c o m p le x e s (T ab le VI) i n d i c a t e t h a t th e m o le c u le s e x i s t a s m o n o n u c le a r
44
s p e c i e s . The X -ra y p o w d e r p h o to g ra p h s s h o w e d d i f f e r e n c e s i n d ic a tin g
t h a t t h e s e c o m p le x e s a re n o t is o m o r p h ic . The in fr a r e d s p e c tru m o f
C u (N N )2 Br2 w a s c o m p a re d w ith t h o s e o f C u(N N )2 C l2 , C u (N N )C l2 , a n d
t e t r a k i s n i t r a t e a n d p e r c h l o r a t e c o m p le x e s w h ic h c o n ta i n b i d e n t a t e l y
c o o r d in a te d n a p h th y r id in e in th e r e g io n 4 0 0 0 -3 0 0 cm \
The lig a n d
m o d e s o f th e b is h a l i d e c o m p le x e s a re l i s t e d in Table V II. The ban d a t
1350 cm * w h ic h o c c u r s in C u (N N )C l2 i s n o t p r e s e n t in th e C u (NN)g Br2
s p e c tru m a n d a n e w b a n d a t 1 1 4 7 c m
-I
th e lig a n d b a n d a t 1 128 cm
-I
h a s a p p e a r e d . The s p l i t t i n g o f
-I
in to tw o b a n d s a t 1128 cm
-I
a n d 1145 cm
h a s a l s o b e e n r e p o r te d (2 6) for dmNN c o m p le x e s in w h ic h 2 ,7 - d im e th y l1,8- n a p h t h y r i d i n e s w e re c o o r d in a te d th ro u g h b o th n itr o g e n s to th e m e ta l
i o n s . The in fr a r e d s p e c tru m o f th e C u (N N )2 Br2 c o m p le x w a s s im ila r to
th e s p e c t r a o f th e t e t r a k i s p e r c h lo r a te c o m p le x e s ( s e e Fig u re 3) in
w h ic h n a p h t h y r i d i n e s w e re c o o r d in a te d th ro u g h b o th n itr o g e n s to th e
m e ta l io n . The s p l i t t i n g o f th e lig a n d b a n d a t 1128 cm * w a s n o t o b ­
s e r v e d in p e r c h lo r a te c o m p le x e s b e c a u s e t h i s re g io n o f th e s p e c tr a
w as
c o v e r e d b y v e r y s tro n g a n d b ro a d b a n d o f p e r c h lo r a te a n io n . The
s p e c t r a o f p e r c h lo r a te c o m p le x e s w e re s u p e r i m p o s a b l e , a p a r t from p e r ­
c h lo r a te a n d n i t r a t e b a n d s , on s p e c t r a o f n i t r a t e c o m p le x e s in w h ic h
th e s p l i t t i n g o f th e 112 8 cm * lig a n d b a n d s w a s o b s e r v e d ( s e e Table
XVIII). The a g r e e m e n t o f th e C u(N N )2 Br2 in fra re d s p e c tru m w ith t h o s e of
c h e l a t e d c o m p le x e s s u g g e s t s t h a t th e n a p h th y rid in e m o le c u le s a re c o ­
o r d in a te d th ro u g h b o th n itr o g e n a to m s to th e m e ta l io n .
The
45
c o p p e r - b r o m in e s t r e t c h i n g f r e q u e n c i e s w e re n o t o b s e r v e d in t h i s s tu d y
s i n c e t h e y w e re b e y o n d th e ra n g e o f th e in s tr u m e n t a v a i l a b l e to u s .
This a l s o i n d i c a t e s t h a t th e b a n d o b s e r v e d a t 2 8 2 (v s,b r) cm * in
C u (N N )^C lg i s c o p p e r - c h l o r i n e s t r e t c h i n g v ib r a tio n s i n c e i t w a s n o t
o b s e r v e d in C u (N N )2 Brg c o m p le x .
The r e f l e c t a n c e s p e c t r a o f C u(N N )gC lg a n d C u(N N )2 Brg in th e
v i s i b l e re g io n a re sh o w n in Fig u re 9 a n d th e a b s o r p tio n b a n d s a re l i s t e d
in T a b le IX. The C u(N N )2 Clg s p e c tru m c o n t a i n s a b ro a d b a n d w ith an
i l l - d e f i n e d maximum in th e re g io n 1 5 0 0 0 -1 3 0 0 0 cm
w h e r e a s th e s p e c ­
trum o f C u (N N )2 Br2 s h o w e d c o m p a r a ti v e ly s h a rp b a n d w ith a b s o r p tio n
maximum a t 13000 cm ^ w h ic h a g a in i n d i c a t e s t h a t th e g e o m e tr ie s o f th e
tw o c o m p le x e s a re n o t s i m i l a r . Above 2000 cm
th e a b s o r p tio n r i s e s
s h a r p l y d u e to c h a r g e t r a n s f e r a n d ligand b a n d s ( s e e Figure 9 a n d Table
IX). S e v e r a l copper(II) c o m p o u n d s w ith d if f e r e n t g e o m e t r ie s a n d v i s i b l e
a b s o r p tio n b a n d (s ) a re l i s t e d for c o m p a r is o n in Table X. The p o s itio n o f
th e a b s o r p tio n b a n d s in copper(II) c o m p le x e s v a r i e s g r e a t l y w ith d if f e r ­
e n t c o o r d in a tio n g e o m e t r i e s . To a s s i g n a g e o m e try to th e C u(N N )2 Br2
from i t s v i s i b l e a b s o r p tio n b a n d i s c l e a r l y n o t p o s s i b l e , b u t th e s p e c ­
trum is s i m i l a r to th o s e o f d i s t o r t e d o c t a h e d r a l c o m p l e x e s . The m olar
c o n d u c ti v ity o f th e C u(N N )2 Br2 in a b s o l u t e m e th a n o l s o lu tio n (T able II)
i n d i c a t e d t h a t th e c o m p le x w a s n o t i o n ic a n d th e in fr a r e d s p e c tru m s u g ­
g e s t e d c o o r d in a tio n o f th e l i g a n d s th ro u g h b o th n i t r o g e n s . Thus a
46
T ab le X
ELECTRONIC ABSORPTION SPECTRA OF SOME Cu(II) HALIDES3
C om pound
G e o m etry
—I
V is ib le Bands , cm
C u ( D m q ) C l^
d ist. o c t.
18690 s h
Cu(Dmq) Br^
d ist. o c t.
T r a n s - C u ( D p q ) 0 C l0^
sq u . p la n ar
T r a n s - C u ( D p q ) 0 Br0
s q u . p la n a r
14925
Cu(Mq) %Clgb
d ist.. o c t.
14700,
C u (M q )2 Br2
d is t. o c t.
16130
C u (M p y )2 C l 20 '
te tr a g o n a l
28000
C u (b ip y )2 Br2G
p y ra m id a l
26700
C u C l2 * 2 N H ^
d is t. o c t. '
14850
CuBr2 • 2 NHgd
d i s t . o c t.
14800
C u C l2P y 26
d i s t . o ct..
14500
C u (4 -M e T )C l2f
d is t. o c t.
14180
14925
18690
14290
12800
.
25600
12800
13300
a R e fe re n c e 44 . ^ D m q= 2,3 - d im e th y lq u i n o x a lin e ; D p q = 2 ,3 d ip h e n y lq u in o x a lin e ; M q = 2 - m e t h y l q u i n o x a l i n e . C R e fe re n c e 45 .
R e fe re n c e 46 . e R e f e r e n c e s 43, 47. ^ 4 - M e t = 4 - m e th y lth i a z o le ;
r e f e r e n c e 48.
47
d i s t o r t e d o c t a h e d r a l g e o m e try for th e c o p p e r(li) io n s u rro u n d e d by four
n itr o g e n s a n d two bro m in e a to m s s e e m s l i k e l y .
C ufdm N N lgC lg a n d C u C d m N N ^ B ^ :— The in fr a r e d s p e c t r a o f th e
o l i v e - g r e e n CuCdmNN^Brg a n d th e b lu e C uCdm N N ^C lg w e re i d e n t i c a l .
a n d a l s o w e re s u p e r im p o s a b le on th e s p e c tru m o f th e brow n
C uC dm N N ^C lg w h ic h w a s o b ta in e d from d e c o m p o s itio n o f th e b lu e d e ­
r iv a tiv e upon e x p o s u r e to s u n lig h t for tw o w e e k s . The lig a n d m odes
w h ic h s h i f t s i g n i f i c a n t l y upon c o o r d in a tio n a n d th e fre e lig a n d v i b r a ­
t i o n s a r e l i s t e d in T a b le XI. The a s s i g n m e n t o f th e lig a n d m o d e s h a s
b e e n r e p o rte d in th e l i t e r a t u r e (7). In th e s p e c t r a o f t h e s e c o m p le x e s
th e lig a n d b a n d a t 112 8 cm * w a s n o t o b s e r v e d a f t e r c o o r d in a tio n and
-I
o n ly o n e s tro n g b a n d a t 1147 cm w a s p r e s e n t . This a p p e a r a n c e o f a
s i n g l e b a n d in th e re g io n 1 1 0 0 -1 2 0 0 cm
i s s im ila r to th e s in g le band
o b s e r v e d a t 1136(s) cm * in C u(N N )g Clg in w h ic h n a p h th y r id in e s w ere
c o o r d in a te d th ro u g h o n e o f th e n itr o g e n s to th e c o p p e r i o n .
This i s in
c o n t r a s t to th e in fr a r e d s p e c t r a o f th e dmNN c o m p le x e s r e p o rte d in the
l i t e r a t u r e (2 6) in w h ic h n a p h th y r id in e s w e re c h e l a t e d a n d s h o w e d two
b a n d s a t 1128 cm * a n d 1145 cm *. The in f r a r e d a b s o r p tio n b a n d s w ere
c o m p a re d w ith t h a t o f th e iro n c o m p le x , Fe(dm N N )g(C lC ^)g (7 ). The
lig a n d b a n d s a t 8 47(vs), 8 05(vs), a n d 778(vs) cm \ w h ic h a re s e n s i t i v e
to c o o r d in a tio n a n d s h i f t to 87 0 (s), 8 5 3 (s), a n d 803(vs) cm * r e s p e c t i v e l y
in iron(II) c o m p le x , w e re o b s e r v e d a s fiv e b a n d s a t 8 6 8 (v s), 815(m, sh),
8 1 0 (s), 8 0 3 (v s), a n d 777(w) cm ^ (T ab le XI) in Cu(dmNN)g+ h a lid e
48
T a b le XI
SELECTED INFRARED ABSORPTIONS (4 0 0 0 -2 50 CM
Band
C u(dm N N )2 C l2
dmNN
) OF Cu(dm N N )2X2
C u(dm N N )2 Br2
I
1532 m
1570 s
1567 s
II
1360 w
1380 s-
1380 s
III
1240 s ,
1255 s
1253 s
IV
1205 m
1220 m
122 0 m
847 v s
868 v s
867 v s
815 m , s h
816 m , s h
V
VI
VII
VIII
• • • «
803 v s
. • e •
IX
778 v s
X
625 m
XI
810 s
805 v s
O» • e
'
' 810 s
802 v s ■
777 w
777 w
648 w
648 w
515 w
514 w
' 457 m
XII
442 m
457 m
XIII
345 m
353 v w
352 vw
XIV
268 w
283 v s , b r
2 80 s ,b r
* The a s s i g n m e n t s are: s, stro n g ; v s , v e r y stro n g ; w, w e a k ; vw, veryw e a k ; m , medium; s h , s h o u ld e r; br, b ro a d .
49
c o m p l e x e s . All t h e s e d a t a s u g g e s t t h a t n a p h th y r id in e s a re c o o rd in a te d
m o n o d e n ta te ly to th e c o p p e r io n in Cu(D m N N )^Clg a n d Cu(dmN N )2 Br2
c o m p le x e s.
The X -ra y p o w d e r p h o to g ra p h s o f b lu e C u (d m N N )2 C l 2 , brown
C u(dm N N )2 C l2 , a n d o l i v e - g r e e n C u(dm N N )2 Br2 were a l l s im i l a r a n d did
n o t s h o w a n y s i g n i f i c a n t c h a n g e s in th e i n t e n s i t y or p o s i t i o n o f the
s p e c t r a l l i n e s , w h ic h i n d i c a t e s t h a t a ll c o m p o u n d s a re i s o m o r p h ic , in
good a g r e e m e n t w ith th e in fr a r e d d a ta . The n a tu re o f th e c o lo r c h a n g e
from b lu e to brow n upon e x p o s u r e to s u n lig h t o f th e C u(dm N N )2 C l2 i s a
v e ry i n t e r e s t i n g p ro b lem b u t h a s n o t b e e n i n v e s t i g a t e d in th is r e s e a r c h .
The C u(dm N N )2 Br2 c o m p le x g a v e a m a g n e tic m om ent of 1.99 B .M . s im i­
la r to th e v a l u e s o b ta in e d for m o n o n u c le a r copper(II) c o m p le x e s (s e e
T a b le V I).
The s p a r in g s o l u b i l i t i e s o f th e a b o v e c o m p le x e s in o r g a n ic s o l ­
v e n t s d id n o t p e rm it v i s i b l e s p e c t r a m e a s u r e m e n t s . The m o la r c o n d u c ­
t i v i t y v a l u e s o f th e c o m p le x e s in DMF s o l u t i o n s i n d i c a t e d t h a t the
c o m p le x e s w e re n o t i o n i c . This s u g g e s t s c o o rd in a tio n o f th e c h lo rid e
a n d bro m id e io n s to th e c o p p e r i o n s .
From in fr a r e d a b s o r p tio n s p e c t r a , m a g n e tic m o m e n ts , and X -ra y
p o w d e r d a ta i t is n o t p o s s i b l e to a s s i g n a c e r ta in g e o m e try to th e c o m ­
p l e x e s , b u t a m o le c u la r m odel s h o w s t h a t th e m e th y l g ro u p s on th e
s u b s t i t u t e d n a p h th y r id in e m o le c u le s w o u ld n o t p e rm it fo rm atio n o f a c i s
s q u a r e - p l a n a r g e o m e try a ro u n d th e c o p p e r a to m . The m o d e l s h o w s a
50
s e v e r e l y h in d e re d s tr u c tu r e for a c i s c o m p le x , w h e r e a s t h i s h in d ra n c e
d o e s n o t p ro h ib it th e m o le c u le from form ing a c is g e o m e try in
C u(N N )£ C ^ ; th e r e f o r e a tr a n s g e o m e try is p r e d ic te d in 2 ,7 -d im e th y l
s u b s t i t u t e d n a p h th y r id in e c o m p l e x e s . The d if f e r e n c e s in c o lo r o f g re e n
Cu(dmNN)2Br2 from C u(N N )2 Br2 a n d th e s i m ila r ity o f th e c o lo r to th e
t r a n s - C u ( p y ) 2 Br2 (g reen ) i n d i c a t e s t h a t th e e n v iro n m e n t o f th e copper(II)
io n s h o u ld be s i m i l a r to t h a t o f th e p y rid in e c o m p le x , i . e . , tr a n s g e o m e ­
try r a th e r th a n c i s . The C u(dm N N )2 C l2 (blue) a l s o h a s a d iff e r e n t c o lo r
from t h a t o f C u(N N )2 C l2 (green) a n d i s s im ila r to t r a n s - C u ( p y ) 2 C l2
( g r e e n is h - b lu e ) w h ic h a g a i n s u g g e s t s a tr a n s g e o m etry for th e
C u(dm N N )2 C l2 c o m p le x . T h e s e o b s e r v a t i o n s a re in g o o d a g re e m e n t
w ith th e m o le c u la r m o d el s u g g e s t e d a b o v e .
C o(N N )2 C l2 =-
The v i s i b l e s p e c tru m o f C o(N N )2 C l 2 in n itr o m e th _1
a n e s o lu tio n s h o w e d fo u r b ro a d b a n d s in th e re g io n 1 7 0 0 0 -1 5 0 0 0 cm
(T ab le IX) w ith m o la r a b s o r p t i v i t i e s o f 3 5 0 - 4 2 0 . This i s in good a g r e e ­
m e n t w ith th o s e re p o rte d fo r o th e r t e t r a h e d r a l co b alt(II) c o m p le x e s (4 9 ).
The a b s o r p tio n b a n d s r e p o r te d for t e t r a h e d r a l te tr a h a l o c o b a lt( I I ) io n s
h a v e b e e n re p o rte d in th e ra n g e 2 3 0 0 0 -1 5 0 0 0 cm
(5 0 ). The b lu e co m ­
p l e x i s s t a b l e in n itro m eth an e. s o lu tio n , b u t n o t in w a t e r o r a b s o lu t e
m e th a n o l. A fter d i s s o l v i n g th e b lu e com p o u n d in w a te r o r a b s o l u t e
m e th a n o l a p in k s o lu tio n , i s o b ta in e d w h ic h i n d i c a t e s t h a t th e com pound
h a s d if f e r e n t m o le c u la r s tr u c tu r e in v a r io u s s o l v e n t s .
51
The in fr a r e d a b s o r p tio n b a n d s in G o(N N )^Clg a re s i m i l a r to th e
C u(N N )g Brg s p e c tru m in w h ic h b id e n t a t e c o o rd in a tio n o f th e lig a n d w a s
su g g e ste d .
Three b a n d s a t 3 1 0 (s), 285(m), a n d 257(m) a r e o b s e r v e d in
th e C o(N N )gC lg s p e c tru m w h ic h c o u ld b e a s s i g n e d to th e c o b a l t c h lo rin e o r c o b a l t - n i t r o g e n s t r e t c h i n g f r e q u e n c i e s . I n s k e e p (51) h a s r e ­
p o rte d t h a t th e m e t a l - n i t r o g e n s t r e t c h i n g f r e q u e n c i e s for c o b alt(II)
c o p p e r ( I I ) , a n d z in c(II) c o m p le x e s o f p h e n a n d b ip y o c c u r in th e re g io n
3 0 0 -2 6 4 cm \ b u t th e in fr a r e d s p e c t r a o f C o(N N )^(C 10^)g • 4 HgO a n d
Co(N N )gN O g)g c o m p le x e s (T a b le s VII a n d XVIII) s h o w e d no b a n d s in
t h i s r e g io n e x c e p t m o d ifie d lig a n d b a n d s . This i n d i c a t e s t h a t th e b a n d s
o b s e r v e d in th e C o(N N )gC lg a re c o b a l t - c h l o r i n e s t r e t c h i n g v i b r a t i o n s .
This is a l s o in a g r e e m e n t w ith t h e lo w c o n d u c ti v ity v a lu e o f th e c o m ­
p le x w h ic h a g a in s u g g e s t s c o o r d in a tio n o f th e c h lo rin e a t o m s .
B a n is te r e t a l . (52) h a v e r e p o rte d th e p r e p a r a tio n a n d c h a r a c t e r i ­
z a ti o n o f a co m p o u n d Co [( C g H 5)^PO Ig (N O g ) 2 a n d from t h e m a g n e tic
d a ta (4.69 B . M . ) t h e y a s s i g n e d a t e t r a h e d r a l s tr u c tu r e for th e c o m p le x .
L a te r , th e m o le c u la r s tr u c tu r e d e te r m in a tio n o f th e c o m p le x by X -ra y
s t u d i e s s h o w e d t h a t th e co b alt(II) w a s s u rro u n d e d by a n ir r e g u la r
a rra n g e m e n t o f s i x o x y g e n a t o m s , e a c h n i t r a t e io n s e r v in g a s a b id e n ­
t a t e lig a n d (10).
A lthough th e m a g n e tic d a ta a n d th e v i s i b l e b a n d s s u g g e s t a t e t r a ­
h e d ra l g e o m e try for th e C o(N N )2 Clg , th e in fra re d s p e c tru m i n d i c a t e s
t h a t th e n a p h th y r id in e m o le c u le s a re c o o r d in a te d th ro u g h b o th n itr o g e n s
52
to th e c o b a lt(II) i o n . The c o n d u c ti v ity v a lu e is i n d i c a t i v e o f n o n - i o n i c
s p e c i e s a n d th e in fr a r e d d a ta s u p p o rt c o o rd in a tio n o f th e c h lo rid e io n s
to th e c o b a l t a to m . This m e a n s t h a t th e c o b a l t atom i s s u rro u n d e d by
fo u r n itr o g e n s from tw o n a p h th y r id in e m o le c u le s a n d tw o c h lo rin e
a to m s . The c o m p le x i s th e re fo re h e x a c o o r d i n a t e , b u t o c t a h e d r a l
g e o m e try s e e m s u n lik e ly in v ie w o f th e t e t r a h e d r a l a p p e a r a n c e o f th e
v i s i b l e s p e c tr u m . T rig o n al p r i s m a t i c g e o m e try is p o s s i b l e in th is c a s e
a n d c a n b e c o r r e l a t e d w ith th e v i s i b l e s p e c tru m in th e fo llo w in g w a y .
The tw o c o o r d in a tin g g ro u p s on n a p h th y r id in e are m uch c l o s e r t o g e th e r
th a n i s u s u a l in c h e l a t e m o l e c u l e s , a n d m ay be c o n s id e r e d in t h i s c a s e
a s a " s l i g h t l y s p l i t " s i n g l e g r o u p . If tw o o f th e le g s o f a trig o n a l p ris m
a re f u s e d in t h i s w a y a n a p p ro x im a te te tr a h e d r o n r e s u l t s . I t is t h e r e ­
fore s u g g e s t e d t h a t t h i s c o m p le x e x h ib its trig o n a l p r i s m a t i c c o o r d in a ­
t i o n , t r e a t i n g th e tw o n itr o g e n s in e a c h n a p h th y rid in e m o le c u le a s
s e p a r a t e c o o rd in a tin g g r o u p s , b u t t h a t th e p ro x im ity o f th e tw o n itr o ­
g e n s l e a d s to a q u a s i - t e t r a h e d r a l e n v iro n m e n t for th e c o b a l t a to m , th u s
a c c o u n tin g for th e v i s i b l e s p e c tr u m . '
The u l t r a v i o l e t a b s o r p tio n s p e c t r a o f h a lid e c o m p le x e s ' in a b s o ­
lu te m e th a n o l s o l u t i o n s a re re p o rte d in T a b le XII.
C o m p a ris o n o f th e
c o o r d in a te d a n d fre e lig a n d s p e c t r a s h o w e d th a t th e re w e re no s i g n i f i ­
c a n t s h i f t s in th e p o s i t i o n o f th e b a n d s a lth o u g h a few e x tr a s h o u ld e r s
w e re o b s e r v e d in C u(N N )C lg a n d Cu(NN)Br2 s p e c t r a .
T h e s e d a ta w e re
53
T ab le XII
ULTRAVIOLET ABSORPTION SPECTRA*
X, nm
v, kK
em a x ' M 1K
nm
v ' kK
32.5
(33.0)
33.1
33.8
(34.5)
(35.2)
(37.9)
38.5
(38.8)
6360
6130
6610
6180
5370
4840
6270
6340
6240
308
(304)
302
(296)
(291)
(285)
(261)
257
(251)
32.4
33.2
(33.7)
(34.5)
(35.1)
38.8
32.5
(32.9)
33.1
(33.8)
(34.4)
(35.1)
(38.3)
38.9
(39.8)
12060
12770
11570
9370
7880
11070
308
(303)
301
(296)
(290)
(284)
257
32.5
(33.0)
33.2
(33.8)
(34.5)
(35.2)
38.9
C o(N N )2 C l 2
301
32.5
33.2
(299)
(296)
(289)
(283)
258
(33.4)
(33.8)
(34.6)
(35.3)
38.8
308
7560
7310
7750
7930
5590
4260
5590
5720
5470
Cu(NN)2 Br2
C u(N N )2 C l 2
309
' 301
(297)
(290)
(285)
258
- m ^1
Cu(NN)Br2
Cu( NN)Cl2
308
(303)
302
296
(290)
(284)
(264)
261
(258)
W
11550
11200
12090
10840
8530
6750
10130
C gH eN g
20550
.21600
20490
19140
14640
10890
15900
309
(304)
301
(297)
(290)
(283)
257
32.4
(32.9)
33.2
(33.7)
(34.5)
(35.3)
.
38.9
5700
5280
5900
5200
4000
2900
4310
54
T ab le XII
X, nm
(c o n tin u e d )
v, kK
6D13X ' M
C u(dm N N )2 C l 2
317
309
303
(297)
(291)
(285)
254
31.5
32.4
33.0
(33.7)
(34.4)
(35.1)
39.4
22250
18300
18100
13100
10400
7700
9400
C u(dm N N )2 Br2
317
309
303
(297)
(290)
(285)
(257)
(239)
31.5
32.4
33.0
(33.7)
315
308
304
(297)
(291)
31.7
32.5
32.9
(33.7)
(34.4)
(285)
(272)"
253
(35.1)
(36.8)
(34.5)
(35.1)
(38.9)
(41.8)
39.5
20600
17250
17000
11900
9100
6350
5000
17000
9200
8760
8700
6070
4400
3000
2600
3800
* P a r e n t h e s e s r e p r e s e n t s h o u ld e r s ; a b s o r p tio n s w e re m e a s u r e d in a b s o ­
lu t e m e th a n o l s o l u t i o n s .
55
n o t u s e d in a n y o f th e s t r u c t u r a l a n a l y s e s b u t are r e p o rte d h e re for
fu tu re r e f e r e n c e .
SUMMARY OF PART I:
Two c o m p l e x e s , C u(N N )C lg a n d Cu(NN)Brg , h a v e b e e n i s o l a t e d .
The d a t a a n a l y z e d i n d i c a t e t h a t t h e s e c o m p o u n d s h a v e t h e s a m e s t r u c ­
t u r e , p r o b a b ly a b i n u c l e a r 1,8- n a p h t h y r i d i n e - b r i d g e d c o m p le x w ith a t
l e a s t o n e a n d p r o b a b ly b o th h a l i d e s c o o r d in a te d .
The c o m p le x e s C u(dm N N )gC lg a n d Cu(dmNN)gBrg h a v e b e e n s y n ­
th e siz e d .
The d a ta o b ta in e d i n d i c a t e c o o rd in a tio n o f th e n a p h th y rid in e
m o le c u le s th ro u g h o n e o f th e n itr o g e n a t o m s . A te tr a c o o r d in a te d
copper(II) io n (two n itr o g e n s a n d tw o h a lid e io n s) w ith t r a n s g e o m etry
for t h e s e c o m p le x e s h a s b e e n s u g g e s t e d .
The in f r a r e d s p e c t r a o f C u(N N )g Brg a n d C u(N N )g Clg p r e v io u s ly
p r e p a r e d b y E nw all w e re e x a m in e d . The s p e c tru m o f th e c h lo rid e for
w h ic h th e s tr u c tu r e i s know n w a s u s e d a s a re fe re n c e p o in t in c o m p a ri­
s o n s o f d a ta on th e o th e r c o m p o u n d s . The brom ide a p p e a r s from th e
d a ta to c o n ta i n c h e l a t e d n a p h th y r id in e s a n d a d i s t o r t e d o c ta h e d r a l
g e o m e try .
F i n a l l y , th e C o(N N )2 Clg c o m p le x w a s p r e p a r e d . The d a ta s u g ­
g e s t a tr ig o n a l p r i s m a t i c g e o m e try for t h e c o m p le x w ith th e n a p h th y r id in e s c h e l a t e d a n d c h lo r id e io n s c o o r d in a te d .
56
Three c o o rd in a tio n ty p e s fo r 1 ,8 -n a p h th y rid in e a n d i t s d e r iv a tiv e s
a re c l e a r l y d i s t i n g u i s h a b l e in t h i s group o f c o m p o u n d s: m o n o d e n ta te ,
a s in CutNlxOgClg a n d in th e dmNN c o m p le x e s ; b i d e n t a t e a n d c h e la te d
to a s i n g l e m e ta l atom a s in C u C N N ^ B ^ a n d C o(N N )2C ^ ; a n d s y n - s y n
b i d e n t a t e , b rid g in g tw o a d j a c e n t m e ta l a to m s a s in C u (N N )C l2 and
Cu(NN)Br2 .
57
PART II.
PERCHLORATE COMPLEXES:
S y n t h e s e s of p e r c h l o r a t e c o m p le x e s from a q u e o u s s o lu tio n s
r e s u l t e d , i n i s o l a t i o n o f th r e e t e t r a k i s 1 ,8 -n a p h th y rid in e t e tr a h y d r a te
c o m p o u n d s o f m a n g a n e s e ( II), Cobalt(II), a n d n ic k e l ( I I ) . Two a n h y d ro u s
t e t r a k i s c o m p o u n d s , C u f N N ^ f C l O ^ g a n d Zn(NN)4 ( C l C ) ^ / w e re o b ­
t a i n e d , a n d tw o c o m p o u n d s o f form ula Z n(N N )^(C lO 4)^ ' 4 H2O and
Ag(NN)ClO4 . R e c r y s t a l l i z a t i o n o f th e co p p er(II) c o m p le x from a m ixture
o f w a t e r a n d a c e t o n e g a v e a c r y s t a l l i n e te t r a h y d r a t e c o m p le x s u i t a b l e
for X -ra y d a ta c o l l e c t i o n .
The a n a l y t i c a l a n d p h y s i c a l d a ta for p e r c h lo r a te c o m p le x e s a re
g iv e n in T a b le III. The m o la r c o n d u c t i v i t y m e a s u r e m e n ts o f th e com ­
p o u n d s in n itr o m e th a n e o r a b s o l u t e m e th a n o l s o lu tio n s e x h i b i t c o n d u c ­
t i v i t y v a l u e s a p p r o p r ia te for t h r e e - i o n s p e c i e s o f th e f i r s t ro w t r a n s i t i o n
m e ta l c o m p le x e s a n d a t w o - i o n s p e c i e s for th e s ilv e r(I) c o m p o u n d .
The in fr a r e d a b s o r p tio n s p e c t r a o f th e c o m p le x e s w e re re c o rd e d in
th e re g io n 4 0 0 0 -2 5 0 cm \
The s e l e c t e d lig a n d m o d es w h ic h c h a n g e
upon c o o r d in a tio n a re l i s t e d in T ab le XIII. The s p e c t r a o f a l l c o m p le x e s ,
a p a r t from Ag(NN)ClO4 , a re i d e n t i c a l a n d th e r e w e re no s i g n i f i c a n t
d if f e r e n c e s from th e s p e c t r a o f th e a n h y d ro u s c o m p o u n d s , e x c e p t th e
l o s s o f th e o x y g e n - h y d r o g e n s t r e t c h i n g b a n d in th e re g io n 3 5 0 0 -1
3100 cm '. The s p e c t r a o f t h e h y d ra te d c o m p o u n d s did n o t c o n ta in a n y
a b s o r p tio n b a n d s a t 700 cm ^ or 575 cm ^ (2 6,53) w h ic h c a n b e a s s i g n e d
to c o o r d in a te d w a t e r v ib r a tio n f r e q u e n c i e s . This i n d i c a t e s th a t the
T ab le XIII
SELECTED INFRARED ABSORPTIONS (4 0 0 0 -2 5 0 CM 1J OF PERCHLORATE COMPLEXES *
Band
NN
I
M n(N N )4 (C lO 4) 2 ' 4 H2O
Co(NN)4 (ClO4) 2 '4 H2O
Ni(N N )4 (ClO4) 2 "
3500 v s , br
3100 v s , br
3300 v s , br
II
1602 v s
1607 v s '
1605 v s
1605 v s
III
1555 v s
1575 s
1572 s
1565 s
IV
1492 v s
1494 v s
1494 v s
1503 v s
V
1228 s
1238 s
1237 s
1242 m
-1085 v s , br
1085 v s , br
1090 v s , br
VI
VII
835 v s
835 v s
835 v s
835 s
VIII
809 v s
803 v s
800 v s
805 v s
IX
773 m , s h
778 v s
782 v s
782 m
X
760 v s
762 s 7s h
760 s
770 m
XI
483 m , s h
«
«
*
480 w
XII
475 s
470 s
462 m
468 m
XIII
402 s
405 m
405 m
420 m
O a
•
T ab le XIII (c o n tin u e d )
Band
Cu(NN) 4 (C 1 0 4) 2 - 4 H 20
I
3600 v s , b r
II
1605
VS
III
1565
IV
1492
V
VI
Zn(NN)4 (C lO 4) 2
Zn(NN)2 (C lO 4) 2 *4 H2O
Ag(NN)ClO
3500 s ,b r
....
1 605 vs
1605 v s
1605
VS
S
1570 s
1565 s
1570
S
S
1500 v s , b r
1505 v s
1505
VS
1240 m
1238 s
1238 s
1240 m
1090 v s , b r
1110 v s , b r
1095 v s , b r
1085
V S yfc
VII
838
VS
838 v s
842 v s
855
S
VIII
805
VS
805 v s
837 s
835
VS
IX
785
S
• 780 v s
800 v s
802
VS
X
760 m
760 s
780 v s
775
S
XI
470
W
475 vw
475 m , s h
490
VW
XII
460
W
470 m
470 m
475 m
XIII
415
W
405 m
425 m
420 m
'
* The a s s i g n m e n t s are: s> stro n g ; v s , v e ry stro n g ; m , m edium ; w, w eak; vw, v e ry w e ak ;
s h , s h o u ld e r; br, b r o a d .
60
w a t e r m o le c u le s e x i s t a s l a t t i c e w a te r in th e c r y s t a l s .
The s im ila r ity ■
o f th e h y d ra te d a n d a n h y d ro u s s p e c t r a (F ig u re 10) i n d i c a t e s t h a t th e
n a p h th y rid in e c o o r d in a tio n is v e ry s i m i l a r in th e two s e r i e s .
The l o s s
o f w a t e r in th e h y d ra te d c o m p o u n d s a t room te m p e ra tu re i n d i c a t e s th a t
th e w a t e r m o le c u le s a re n o t ti g h t l y bou n d in th e c r y s t a l s , a n d h e n c e
u n c o o r d in a te d , fu rth e r s u p p o rtin g th e in fr a r e d d a t a . The in fr a r e d s p e c ­
tr a o f t h e s e c o m p o u n d s a re a l s o i d e n t i c a l w ith th e s p e c tru m of
a n h y d ro u s C u (N N )^ (C lO iJ)2 / w h ic h is is o m o rp h ic w ith F e(N N )^ (C lO iJ)2
(I) in w h ic h th e n a p h t h y r i d i n e s a re c h e l a t e d to th e iro n ato m (Figure 3).
The s i m i l a r i t y o f th e in f r a r e d s p e c t r a , a s w e ll a s th e s i m i l a r i t y o f th e
v i s i b l e s p e c t r a , s u g g e s t s t h a t th e n a p h th y r id in e s a re c o o r d in a te d
th ro u g h b o th n itr o g e n s to th e m e ta l io n s in th e e n tir e s e r i e s o f h y d ra te d
a n d a n h y d ro u s p e r c h lo r a te c o m p l e x e s . The s i l v e r c o m p le x is an e x c e p ­
tio n w h ic h w ill b e d i s c u s s e d in a s e p a r a t e p a r a g r a p h .
The p e r c h lo r a te io n in fr a r e d b a n d s in a ll p e r c h l o r a t e c o m p le x e s
a re s i m i l a r to th e fre e io n b a n d s a n d th e r e i s no i n d i c a t i o n th a t p e r ­
c h lo r a te io n i s c o o r d in a te d to th e c e n t r a l m e t a l s .
The d i f f u s e - r e f l e c t a n c e s p e c t r a o f c o b alt(II), n ic k e l(II), and
co p p er(Il) c o m p le x e s a re l i s t e d in T a b le XIV.
The p o s i t i o n s o f th e
b a n d s a re v e ry s im i l a r to th o s e r e p o r t e d for o c ta h e d r a l c o m p le x e s (7,50,
54). The b a n d s for th e a n h y d ro u s c o m p l e x e s , t e t r a h y d ra te c o m p le x e s ,
a n d m e ta l p e r c h lo r a te h e x a h y d r a te s a re l i s t e d for c o m p a r is o n . The
d i f f u s e - r e f l e c t a n c e s p e c t r a o f th e C u (N N )^(C lO iJ )2 ' 4 H2O a n d
61
I.....i I
L ( C I O jl)0 ,..M nO
---- - H
I . ... L
uxW j ^ i F1V e
- i- r - r : I ;.. 4 *:t—:j”
Fig u re 10.
In fra re d S p e c tra of C u ( C g H g N g ) ^ C lO j^ g ' 4 H^O and
C u (C 8 H 6N 2) 4(C lO 4) 2 .
62
Table XlV
DIFFUSE REFLECTANCE SPECTRA OF PERCHLORATE COMPLEXES (C M - 1 )
Com pound
Bands
C o(N N )4(C lO 4) 2 • 4 H2O
28200 s h , 2 5300 s h , 21400, 20000
C o(N N )4 (C lO 4) 2
24400 w, 20600 s h , 18900, 16700 sh
C o (C lO ^ )2 ' GH2O
25000 S b , 21300 s h , 19700
N i(N N )4 (O lO 4) 2 • 4 H2O
26000 s h , 15500, 13800 sh
N i(N N )4 (C lO 4) 2
16300
N i(C lO 4) 2 • GH2O
25400, 21800 s h , 18900 s, 15400, 14000
C u(N N )4 (C lO 4) 2 • 4 H 2O
16800
C u(N N )4 (C lO 4) 2
16700
C u (C lO 4 ) 2 • GH2O
13300
T ab le XV
ELECTRONIC ABSORPTION SPECTRA
OF PERCHLORATE COMPLEXES (C M -1) *
In a c e t o n i t r i l e s o lu tio n
Bands
M n(N N )4 (C lO 4) 2 • 4 H2O
2500 sh(10), 24300 sh(7), 23800 sh(5)
C o(N N )4 (C lO 4) 2 • 4 H 2O
25000 sh (3 5 ), 23700 sh(17), 19600 sh(145),
18500(210), 16700 sh(40)
N i(N N )4 (C lO 4) 2 • 4 H 2O
26300 (45), 16150 (17)
C u(N N )4 (C lO 4) 2 • 4 H2O
27250 sh (3 5 ), 15750(80)
In n itr o m e th a n e s o lu tio n
M n(N N )4 (C lO 4) 2 * 4 H2O
26000 (40), 23700 Sh(IO)
C o(N N )4 (C lO 4) 2 • 4 H2O
26800 (100), 19500 sh(250), 1 8 5 0 0 (3 5 0 )
N i(N N )4 (C lO 4) 2 • 4 H2O
2 6 0 0 0 (6 0 ), 15850(14)
C u (N N )4 (C lO 4) 2 • 4 H2O
26000 (300), 16100 (125)
* P a r e n t h e s e s r e p r e s e n t m o la r a b s o r p t i v i t i e s .
.
63
C u(N N )^ (C IO ^ )2 in th e v i s i b l e re g io n s h o w s i m i l a r a b s o r p tio n b a n d s
w ith m ax im a a t 16800 cm
-I
-I
a n d 16700 cm r e s p e c t i v e l y .
This a g a in i n ­
d i c a t e d t h a t th e g e o m e try o f th e c o p p e r io n in b o th c o m p le x e s i s i d e n t i ­
c a l w h ic h is in g o o d a g r e e m e n t w ith t h e in fr a r e d a b s o r p tio n d a t a . The
v i s i b l e a b s o r p tio n b a n d s o f th e m e ta l n a p h th y rid in e c o m p le x e s a p p e a r
a t h ig h e r f r e q u e n c i e s th a n th o s e o f m e ta l p e r c h lo r a te h e x a h y d r a te s
w h ic h i n d i c a t e s t h a t n a p h th y r id in e h a s a h ig h e r lig a n d f ie ld s tr e n g th
t h a n w a t e r . This i s in a g r e e m e n t w ith e a r l i e r w ork by H e n d ric k e r a n d
Bodner (7), w ho h a v e d e te rm in e d th e 10 Dq v a l u e s o f dmNN in th e c o m ­
p l e x e s o f n ic k e l(II), iron(II), a n d c o b a lt(II) w ith s to ic h io m e t r y
O -L
M(dmNN) ,g a n d c o n c lu d e d t h a t dmNN h a s a lig a n d fie ld s tr e n g th s i m i ­
l a r to p y r i d i n e .
The s o lu tio n s p e c t r a in a c e t o n i t r i l e a n d n itr o m e th a n e o f p e r c h lo r ­
a t e c o m p le x e s o f t r a n s i t i o n m e ta ls c o n ta in in g l e s s th a n t e n d e le c tr o n s
a re r e p o r te d in T ab le XVI. C o m p a ris o n o f th e d i f f u s e - r e f l e c t a n c e a n d
s o lu tio n s p e c t r a o f th e c o m p le x e s s h o w s t h a t th e p o s i t i o n s o f th e b a n d s
c h a n g e c o n s i d e r a b l y , in d i c a t i n g t h a t th e l i g a n d s a re c o o r d in a te d d if f e r ­
e n tly in s o l u t i o n . The m o la r a b s o r p t i v i t y o f th e c o m p le x e s a s w e ll a s
th e b a n d p o s i t i o n s c h a n g e in b o th a c e t o n i t r i l e a n d n itr o m e th a n e s o l u ­
t io n s w h ic h is i n d i c a t i v e o f th e v a r i a b l e c o o rd in a tio n a b i l i t y o f th e
so lv e n t.
B e c a u s e o f th e l o s s o f w a te r o f h y d ra tio n in h y d r a te d p e r c h lo r a te
c o m p l e x e s , a c c u r a t e X -ra y p o w d e r d a t a w e re v e ry d i f f i c u l t to c o l l e c t
64
w ith th e e q u ip m e n t a v a i l a b l e . I t w a s d e c id e d to o b ta in X -ra y s in g le
c r y s t a l d a t a b y a s p e c i a l p ro c e d u re in o rd e r to p r o t e c t th e co m p o u n d s
from d e h y d r a tio n d u rin g th e p e rio d t h a t th e c o m p o u n d s w e re e x p o s e d to
th e X - r a y b e a m . T h e r e f o r e , X -ra y s i n g l e c r y s t a l d a ta fo r h y d ra te d m a n g a n e s e ( I I ) , c o b a lt(II), n ic k e l(II), a n d copper(II) c o m p le x e s w e re o b ­
t a i n e d by m o u n tin g th e c r y s t a l i n s i d e a s e a l e d g l a s s c a p i l l a r y c o n t a i n ­
in g a s m a ll a m o u n t o f w a t e r or m o th e r liq u o r . The d a t a w e re c o l l e c t e d
O
b y W e i s s e n b e r g m e th o d s u s in g CuKct (X= 1.54A) r a d i a t i o n . C o m p a riso n
o f th e film d a t a o f th e c o m p o u n d s s h o w e d t h a t o n ly th e c o m p le x e s o f
m a n g a n e s e ( II) a n d Cobalt(II) w e re i s o m o r p h ic , in c o n t r a s t to d a ta r e ­
p o rte d in th e l i t e r a t u r e , in d i c a t i n g t h a t a ll a n h y d ro u s t e t r a k i s com ­
p o u n d s from m a n g a n e s e ( II) to c o p p er(II) w e re is o m o r p h o u s .
The s p a c e
group a n d c e l l p a r a m e te r s w e re o b ta in e d to v e rify t h i s u n e x p e c te d
s t r u c t u r a l v a r i a t i o n . C e ll d im e n s io n s w e re d e te rm in e d b y th e m eth o d s
g iv e n b y B uerger (55) from r o ta tio n a n d W e i s s e n b e r g p h o to g r a p h s . The
film d a t a i n d i c a t e d t h a t a l l c o m p le x e s c r y s t a l l i z e d in m o n o c lin ic c e l l s
c e l l s e x c e p t th e n ic k e l(Il) c o m p le x , w h ic h c r y s t a l l i z e d in a t r i c l i n i c
c e ll.
C o b alt(II) a n d Tnanganese(II) c o m p le x e s w e re is o m o r p h ic , as
n o te d a b o v e . The c r y s t a l l o g r a p h i c d a t a for a ll m o n o c lin ic c o m p le x e s
a re l i s t e d i n T a b le XVI. The c r y s t a l d e n s i t y o f th e co p p er(II) c o m p le x ,
Dm = 1.52 gem
m e a s u r e d b y f l o t a t i o n , i n d i c a t e d t h a t t h e r e are four
m o l e c u l e s in t h e u n it c e l l .
C l e a r f ie l d e t a l . (3) h a v e re p o r te d two
m o le c u le s p e r u n it c e l l for th e F e f N N ^ f C l O ^ g w h ic h w a s is o m o rp h o u s
65
T ab le XVI
CRYSTALLOGRAPHIC DATA OF PERCHLORATE COMPLEXES
C om pound
S p a c e Group
C u(N N )4 (C lO 4) 2 -4 H 2O
6 a n g le
a(A
b(%)
c(&)
Ce ° r C2/ c
~88°
.15.83
11.55
17.06
C2 / m - C2 ° r Cm
- 90°
15.85
12.90
8.45
Co (NN )4 (ClO4) 2 '4 H2O
C z/m 'C gO rC m
-90°
15.85
12.90
8.45
Zn(NN)4 (C lO 4) 2
^ l/c
~89°
17.05
11.16
16.40
M n(N N )4 (C lO 4) 2 *4 H 2O
w ith th e c o r r e s p o n d in g copper(II) c o m p o u n d . The Iron(II) c o m p le x c r y s ­
t a l l i z e d in a t r i c l i n i c c e l l w ith s p a c e group P l . The w ork o f Bodner a n d ■
H e n d r ic k e r (I) w ith a n h y d ro u s t e t r a k i s 1 ,8 -n a p h th y rid in e c o m p le x e s i n ­
d i c a t e d t h a t th e s t r u c t u r e s o f a l l c o m p o u n d s from m a n g a n e s e (II) to
co p p er(II) w e re i d e n t i c a l , a n d zin c(II) w a s v e ry s i m i l a r . O u r d a ta c o n ­
firm th e is o m o rp h is m on C u(N N )4 (C lO ^ ) 2 a n d C o(N N )4 (C lO 4) 2 and
i n d i c a t e t h a t Zn(NN)4 (C lO 4) 2 d o e s in d e e d h a v e a s o m e w h a t d iff e r e n t
s t r u c t u r e . The zin c(II) c o m p le x c r y s t a l l i z e s in a m o n o c lin ic c e ll w ith
s p a c e group P2 y c a n d p a n g le o f 8 9 ° w h ic h i s in c o n t r a s t to th e p o w d e r
d a t a r e p o r te d e a r l i e r , a lth o u g h c r y s t a l l i z a t i o n from a q u e o u s s o lu tio n
m ay h a v e in f l u e n c e d th e c h a r a c t e r o f t h e c r y s t a l . The 8 a n g le m e a s u re d
a n d c a l c u l a t e d from z e ro l e v e l W e i s s e n b e r g p h o to g ra p h s g a v e a v a lu e
o f 8 8 - 9 0 ° for a l l c o m p l e x e s .
66
Some a d d i t i o n a l in fo rm a tio n a b o u t th e g e o m e try o f th e c a tio n c a n
b e o b ta in e d from t h e s e d a t a . The m u lt i p l i c i t y o f th e g e n e r a l p o s itio n in
C ^ /m o r C 2 / c is e i g h t - f o l d ; t h a t o f th e g e n e r a l p o s i t i o n in C 2 , C ^ , o r
Cm i s f o u r - f o ld . The d e n s i t y m e a s u r e m e n ts o f C u (N N )^ (C 1 0 ^ )2 • 4 H2 O
i n d i c a t e s t h a t th e re a re fo u r m o le c u le s p e r u n it c e l l .
S in c e th e s im i­
l a r i t y in c e l l d im e n s io n s to th e c o b a l t a n d m a n g a n e s e c o m p o u n d s s u g ­
g e s t s a c l o s e s t r u c t u r a l s i m i l a r i t y o n e c a n d e d u c e t h a t th e num ber o f
m o le c u le s p e r u n it c e l l s h o u ld b e tw o in t h e s e l a t t e r c a s e s . If in t h e s e
tw o c o m p o u n d s ( c o b a l t a n d m a n g a n e s e ) th e s p a c e group i s C 2 / ,
th e
c o m p le x w o u ld th e n b e r e q u ire d to h a v e 2 /m sy m m e try . In v ie w o f th e
d e m o n s t r a t e d s i m i l a r i t y o f t h e i r in f r a r e d s p e c t r a to t h a t o f
F e (N N )^ (C lC ^ )2 , w h ic h d o e s n o t e v e n a p p r o a c h 2 /m s y m m e try , th is
s e e m s u n l i k e l y . In C m o r C 2 th e c o m p le x w o u ld be r e q u ir e d to h av e 2
o r m s y m m e try , b o th o f w h ic h a re a p p r o a c h e d by th e iro n c o m p le x .
S in c e th e s a m e sy m m e try i s re q u ire d o f th e c o m p le x b y th e s p a c e group
in t h e s e tw o c o m p l e x e s , a n d s i n c e th e s i m ila r ity in c e l l d im e n s io n s
s u g g e s t s a s im i l a r s tr u c tu r e to Cu(,N N )^(C10^)2 ' 4 H2O , i t s e e m s p r o b ­
a b le t h a t c o p p e r l i e s o n s p e c i a l p o s i t i o n s in t h i s c o m p o u n d , w h ich
w o u ld r e q u ir e t h a t C 2 ,
a c e n t r i c s p a c e group be th e c o r r e c t o n e .
C e n t r ic c o m p o u n d s a re e a s i e r to s tu d y th a n a c e n t r i c , a n d m o n o c lin ic i s
g e n e r a l l y e a s i e r th a n t r i c l i n i c ; h e n c e a s tr u c tu r e d e te r m in a tio n on th e
c o p p e r co m p o u n d s e e m s l i k e l y to y ie ld b e t t e r d a ta o n th e c o o rd in a tio n
g e o m e try t h a n w a s o b ta in e d from th e d e te r m in e d iro n c o m p le x .
67
The a n h y d ro u s z in c c o m p le x a p p e a r s to h a v e four m o le c u le s p e r
u n it c e l l , from c o m p a r is o n s o f th e c e l l d i m e n s i o n s , a n d h e n c e one
m o le c u le in a g e n e r a l p o s i t i o n . The c o m p a r a tiv e e a s e o f d e te r m in a tio n
in a m o n o c lin ic s p a c e group c o m p a re d to a t r i c l i n i c o n e s u g g e s t s t h a t
t h i s m ay a l s o be a good co m pound for s tr u c tu r e s tu d y .
Z n f N N ^ C l O ^ g ' 4 H2O : -
The in fr a r e d s p e c tru m o f
Zn(NN)2 (C lO ^ )2 • 4 H 2O i s s im ila r to t h o s e o f th e o th e r h y d r a t e d t e t r a k i s
c o m p l e x e s . There i s no i n d ic a tio n t h a t p e r c h lo r a te a n io n s or w a te r
m o le c u le s a re c o o r d in a te d to th e z in c (Il) i o n . The s i m i l a r i t y o f the
in fr a r e d a b s o r p tio n b a n d s s u g g e s t s t h a t th e n a p h th y r id in e s are c o o r d i­
n a te d th ro u g h tw o n itr o g e n s to th e c e n t r a l m e ta l. This s u g g e s t s th a t
zin c(II) io n i s s u rro u n d e d by four n itr o g e n a to m s . S in c e te tr a h e d r a l
g e o m e try for fo u r c o o rd in a tio n is u s u a l for z i n c ( I I ) , a t e t r a h e d r a l
a r r a n g e m e n t for t h i s c o m p le x i s s u g g e s t e d .
A g (N N )C lO ^ :-
The s p e c tru m o f th e Ag(NN)ClO4 c o m p le x i s d i f f e r ­
e n t from t h o s e o f th e t e t r a k i s a n d b is p e r c h lo r a te c o m p l e x e s . The
lig a n d b a n d s a re s im ila r to th e s p e c tru m o f th e C u(N N )2 C l 2 in w h ic h
n a p h th y r id in e s a re c o o r d in a te d th ro u g h o n e of th e n itr o g e n s to th e
c o p p e r a to m . The p e r c h lo r a te b a n d s a re i d e n t i c a l to th e fre e an io n
b a n d s w h ic h i n d i c a t e s t h a t th e p e r c h lo r a te io n is n o t c o o r d in a te d to th e
s ilv e r(I) io n . H o w e v e r th e d a ta o b ta in e d for t h i s c o m p le x i s i n s u f f i c i e n t
to s u g g e s t a n y p o s s i b l e g e o m e try fo r th e c o o rd in a tio n to t h e s ilv e r(I)
io n .
68
The u l t r a v i o l e t a b s o r p tio n b a n d s o f th e c o m p le x e s in a b s o lu t e
m e th a n o l s o l u t i o n s a n d t h e i r m o la r a b s o r p t i v i t i e s a re l i s t e d in Table
XVII. C o m p a ris o n o f th e fre e a n d c o o r d in a te d lig a n d b a n d s s h o w s no
s i g n i f i c a n t s h i f t s in th e p o s i t i o n s o f a n y o f th e b a n d s , a lth o u g h a few
e x tra s h o u ld e r s a p p e a r in th e c o m p l e x e s .
The free lig a n d b a n d a t
38900 cm * a p p e a r s a t a s o m e w h a t lo w e r f r e q u e n c y , 37700 cm- * in th e
s ilv e r(I) c o m p o u n d , b u t th e s i g n i f i c a n c e o f t h i s s h if t i s u n c l e a r a t
p re se n t.
SUMMARY OF PART I I .
T e tr a k is p e r c h l o r a t e c o m p le x e s o f m a n g a n e s e ( I I ) , c o b a lt( I I ) ,
n i c k e l ( I l ) , a n d c o p p er(II) w ith 1 ,8 -n a p h th y rid in e o f th e g e n e r a l formula
M (N N )^(C lO zI) 2 ' 4 HgO h a v e b e e n p r e p a r e d . From c o m p a r is o n o f th e
d a t a w ith t h o s e o f a n h y d ro u s t e t r a k i s c o m p o u n d s r e p o r te d in th e l i t e r a ­
t u r e , c h e l a t i o n o f th e lig a n d w a s e s t a b l i s h e d in a ll c a s e s . All t h e s e
c o m p le x e s c r y s t a l l i z e d in m o n o c lin ic c e l l s e x c e p t th e n ic k e l(II) com ­
p o u n d w h ic h i s t r i c l i n i c .
Zinc(II) io n forms a b is c o m p l e x , . Z n ( N N ^ tC I O zI)2 ' 4 H g O . The
s i m i l a r i t y o f th e lig a n d c h e l a t i o n w ith th e t e t r a k i s h y d r a te d co m pounds
is d is c u s s e d .
!D od ecah ed ral g e o m e try fo r t h e t e t r a k i s c o m p le x e s a n d
t e t r a h e d r a l g e o m e try for Zn(N N )g(C lC z|)g • 4 HgO h a s b e e n p ro p o s e d .
69
T a b le XVII
ULTRAVIOLET ABSORPTION SPECTRA *
X, nm
s max
m av, M-1 K
CSI
O
O
M n(N N ) 4
v, KK
4 HgO
X, nm
v, kK
e
max
, M"
C o(N N )4 (C lO 4) 2 • 4 H 2 O
307
32.6
22700
308
32.5
■22500
301
33. 2
23800
300
33.3
25100
(296)
(33.8)
20900
(295)
(33.9)
20900
(290)
(34.5)
17100
(290)
(34.5)
16400
(283)
(35.3)
11700
(283)
(35.5)
11800
(272)
(36.8)
12300
(276)
(36.2)
10900
(269)
(37.2)
13700
(271)
(36.9)
13000
(264)
.(37.9)
15700
(263)
(38.0)
16100
257
3 8. 9
17400
258
38.7
17300
Ni(NN) 4 < C 1 0 4>2 ' 4 H g O
Cu(NN) 4<C104 ) 2 ' 4 H 2 O
307
32.6
22300
308
32.5
38300
301
33. 2
23400
300
33.3
. 40400
(297)
(33.7)
20600
(295)
(33.9)
35300
(289)
(34.6)
15800
(290)
(34.5)
28400
(283)
(35.3)
11800
(283)
(35.3)
21200
(277)
(36.1)
10700
(274)
(36.5)
21700
(272)
(36.8)
12200
(269)
(37.2)
25400
(269)
(37.2)
13400
258
38.7
30000
257
3 8. 9
17300
70
TableXVIl (c o n tin u e d )
A., nm
v, kK
Gmax'
Zn(NN)4 (C lO 4) 2
307
300
3 3. 3
(295)
(33.9)
(289)
(34.5)
(35.2)
(36.5)
(37.0)
(284)
(274)
(270)
258
32.6
•
38.8
22900
24000
21100
15800
12100
11400
13200
17600
Zn(NN)2(C lO 4) 2 ' 4 H2O
301
33. 2
(296)
(33.8)
(289)
(34.6)
10700
11250
9870
7300
(284)
(35.2)
5370
(276)
(36.2)
(271)
(36.9)
259
38.6
5230
6120
8010
308
32.5
Ag(NN)ClO4
309
300
32.4
(296)
(33.8)
(291)
(34.4)
(35.1)
(37.0)
37.7
(285)
(270)
2 65
33. 3
* P are n th e se s d e sig n a te s h o u ld e rs .
6100
6300
5900
4200
4000
4600
4800
71
A s i l v e r c o m p o u n d , Ag(NN)ClO4 , h a s b e e n i s o l a t e d a n d from th e
in f r a r e d d a ta m o n o d e n ta te c o o rd in a tio n of th e lig a n d h a s b e e n t e n t a t i v e ­
ly a s s ig n e d .
The a n h y d ro u s t e t r a k i s c o m p le x e s p r e v io u s ly re p o rte d h a v e b e e n
p re p a r e d for c o m p a r is o n , a n d th e s t r u c t u r a l d a ta for t h e s e co m pounds
h a s b e e n c o n firm e d a n d e x p a n d e d .
72
PART H I. NITRATE COMPLEXES
T r a n s itio n m e ta l n i t r a t e c o m p le x e s o f 1 ,8 -n a p h th y rid in e w e re i s o ­
l a t e d e i t h e r from a q u e o u s o r o r g a n ic s o l u t i o n s . C o b alt(II) a n d zinc(II)
form t e t r a k i s h e x a h y d r a te s ; m a n g a n e s e ( II), Cobalt(II), a n d copper(II)
form a n h y d ro u s b is c o m p le x e s ; a n d n ic k e l(II), co p p er(II), a n d zinc(II)
form c o m p le x e s o f u n iq u e s to ic h io m e t r y . X -ra y s in g le c r y s t a l d a ta i n ­
d i c a t e s t h a t th e tw o h e x a h y d r a te s a re n o t i s o m o r p h ic , a n d th e a n h y ­
d ro u s b is c o m p o u n d s a l s o e x h ib it e n t i r e l y d if f e r e n t c r y s t a l s t r u c t u r e s .
The a n a l y t i c a l a n d p h y s i c a l d a t a on n i t r a t e c o m p le x e s are g iv e n
in T ab le IV. The m o la r c o n d u c t i v i t i e s o f a l l th e c o m p le x e s w e re d e t e r ­
m in ed in a b s o l u t e m e th a n o l s o l u t i o n s . The v a l u e s i n d i c a t e a t h r e e - i o n
s p e c i e s for a l l f i r s t ro w t r a n s i t i o n m e ta l c o m p le x e s a n d a tw o-ions p e c i e s for th e s ilv e r(l) co m p o u n d . T h e s e c o m p o u n d s th e r e f o r e a p p e a r
to io n iz e c o m p le te ly in s o lu tio n a lth o u g h s e v e r a l o f them c o n ta in c o ­
o r d in a te d n i t r a t e i o n , a s w ill be d i s c u s s e d b e lo w .
C u(N N )4 (N O 3) 2 -G H 2O a n d Zn(NN)4 (NO3) 2 ' 6 HgO: — The in fra re d
a b s o r p tio n b a n d s o f th e c o m p le x e s a re l i s t e d in Table XVIII. The
a s s i g n m e n t s o f th e lig a n d b a n d s a re th o s e re p o rte d in th e lite r a tu r e
(3 7 ). The b a n d s IV, V, a n d XIV a re c h a r a c t e r i s t i c o f n i t r a t e io n . The
s p e c t r a o f t h e s e c o m p o u n d s s h o w e d s p l i t t i n g o f th e lig a n d b a n d a t
-I
-I
-I
112 8 cm to tw o b a n d s a t 112 8 cm a n d 1147 cm . This s p l i t t i n g o f th e
lig a n d b a n d is o b s e r v e d o n ly in c o m p le x e s c o n ta in in g n a p h th y rid in e
m o le c u le s c o o r d in a te d th ro u g h b o th n itr o g e n ato m s a s h a s b e e n
T ab le XVIII
SELECTED INFRARED ABSORPTIONS (4 0 0 0 -2 5 0 CM™1) OF NITRATE COMPLEXES *
Band
NN
Ni(NN)2(NO3)2 MH2O C o (N N ^ N O 3)2 ' 6 H2O Zn(NN)4 (NO3)2 • OH2O Ag(NN)NO3
I
3300 v s , b r
3400 v s , b r
3400 v s , b r
.
0
.
0
II
1555 s
1580 s
1570 s
1565 s
1572 s
III
1492 v s
1507 v s
1502 v s
1500 vs
1500 v s
IV
••••
1390 v s , b r
1395 v s , b r
1390 v s , b r
1385 v s , b r
VI
1275 m
1275 m
12 80 w
1275 w
1270 m
VII
1228 s
1240 s
1240 m
1240 m
1235 m
VIII
... *
1147 m
1150 m
1150 m
Of i f i O
IX
1045 s
1068 s
1068 s
1068 s
1060 v w
X
1027 m
1045 s
1040 w
1035 w
1032 w
XI
985 w
995 s
980 v w
975 vw
Of i f i
XII
970 w
975 v s
965 v w
960 w
Of i O
XIII
953 w
948 s •
945 v w
Of i O
O O O
XIV
...
82 7 s
830 s
828 s
825 s
XV
772 w, sh
s
s
vs
m
vs
785 s
762 m
783 s
760 s
772 s
405 w
V
XVIII
XIX
600 w
•••
782
772
690
630
575
XX
400 m
420 m
XVI
760 s
XVTI
'
fi
O O
B O .
O O O
» 0 0
630 w
630 w
Of i f i
...
Of i O
Of i O
405 w '
410 vw
T a b le XVIII (c o n tin u e d )
Band
NN
M n(N N )2(N O 3) 2
C o(N N )2 (N O 3) 2
C u(N N )2 (N O 3) 2
II
1555 s
1585 s
1580 s
1575 m
1570 m
III
1492 v s
1500 v s
1505 v s
1503 v s
1505 v s
IV
e
•
•
e
1390 y s , b r
1385 v s , b r
1380 v s , b r
1390 v s , br
V
•
•
•
•
1315 v s
a
a
»
VI
1275 m
1265 v s
1270 s , s h
1268 s
1270 vw
VII
1228 s
1238 s
1242 m
1240 m
VIII
»
1147 s
1145 m , s h
1150 m
IX
1045 s
1065 w
1065 s
1060 m
1065 m
X
1027 m
1035 s
1032 m
1018 s
1038 w
XI
985 w
«
a
•
O- 6
a
o
o
a
9 75 vw
XII
970 w
•
«
•
«
•
a
o
a
9 60 vw
XIII
953 w
958 w
958 w
e
o
e
828 s
825 s
810 s
830 s
787 s
C u (N N )2 16( N 0 3
I
O •
•
. 1238 s
1135 s , s h
'
•
»
*
*
*
*
a
a
a
0
a
a
XIV
o
XV
772 w ,s h
780 s
782 v s
785 v s
XVI
760 s
740 w
•
O •
748 v w
a
a
a
XVII
e
«
a
a
a
a
*
a
XVIII
600 w
642 m
628 m
XIX
•
•
555 m
400 m
415 w
XX
o
e
o
e
o
a
a
e
'
a
e
625 v w
630 w
550 w
550 vw
550 w
42 5 m
422 w
420 m
* T h e a s s i g n m e n t s are: s, Strong; v s , v e ry stro n g ; m, medium; w, w eak; vw, v e ry w e ak ;
br, b ro ad ; s h , s h o u ld e r .
75
d i s c u s s e d in e a r l i e r s e c t i o n s o f t h i s t h e s i s . This i n d i c a t e s t h a t th e
n a p h th y r id in e s a re c h e l a t e d in t h e s e c o m p o u n d s to th e c o b alt(II) and
z in c(II) i o n s . The s p e c t r a o f th e a b o v e c o m p le x e s a re s u p e r im p o s a b le
on th e lig a n d b a n d s o f th e c o rre s p o n d in g m e ta l p e r c h lo r a te c o m p l e x e s ,
e x c e p t for th e n i t r a t e a n d p e r c h lo r a te a n io n b a n d s , w h ic h a l s o s u p p o rts
th e a b o v e c o n c l u s i o n . The n itr a te io n b a n d s a re s im i l a r to th o s e o f fre e
a n i o n , i n d ic a tin g t h a t n i t r a t e io n s a re n o t c o o r d in a te d .
The d i f f u s e - r e f l e c t a n c e s p e c tru m o f C o C N N ^ N O g ^ ° 6 H^O
(T ab le XIX) is v e ry s i m i l a r to th e c o r r e s p o n d in g p e r c h lo r a te c o m p le x ,
C o(N N )4 (C lO 4) 2 *4 H 2O (T able XV) in th e v i s i b l e re g io n w h ic h a g a in
s u g g e s t s c h e l a t i o n o f th e lig a n d a n d a d o d e c a h e d r a l g e o m e try for th e
m e ta l io n in b o th o f t h e s e c o m p le x e s s i m i l a r to th a t in th e p e r c h lo r a te
com pounds.
N i(N N )2 (N O g)2 • 4 H 2O : -
The in f r a r e d s p e c tru m o f th e
N i(N N )2 (N O g)2 • 4 H2O c o m p le x s h o w e d s i g n i f i c a n t d if f e r e n c e s w hen
c o m p a re d w ith t h a t o f th e p e r c h lo r a te c o m p le x . Some n e w i n te n s e
b a n d s w e re o b s e r v e d a t 9 9 5 (s), 9 7 5 (v s), a n d 575(vs) cm \
These bands
w e re n o t o b s e r v e d in 1 ,8 -n a p h th y rid in e c o m p le x e s d i s c u s s e d in th e
e a r l i e r p a r t o f t h i s t h e s i s , w h ic h s u g g e s t s a d iff e r e n t c o o rd in a tio n
g e o m e try for t h i s c o m p le x . The tw o v e ry s tro n g b a n d s in t h e n ic k el(II)
c o m p le x s p e c tru m a t 690 cm * a n d 575 cm ^ a re i n d i c a t i v e o f c o o rd in a te d
w a t e r (2 6 ,5 6 ). N o n e o f th e o th e r c o m p o u n d s p re p a re d in t h i s work s h o w
a n y e v id e n c e o f c o o r d in a te d w a t e r . This c o m p le x a p p e a r s to be u n i q u e .
76
T ab le XIX
REFLECTANCE SPECTRA OF NITRATE COMPLEXES (C M - 1 )
C om pound
Bands
C o fN N y N O g ^
25600 s h , 24100 w, 2 0 8 0 0 , 1 9 8 0 0 , 18700 s h
C o(N N )4 (N O 3) 2 - S H 2O
25300 w , 2 1 5 0 0 , 20000
Co(NO3) 2 -GH2O
25000 s h , 21700 s h , 2 0 0 0 0 , 16700 sh
C u(N N )2 16( N 0 3) 2
25000 s h , 24000 s h , 15900
Cu(NO3) 2 - S H 2O
16100 s h , 1 4 3 0 0 , 13200 s h
N i(N N )2 (N O 3) 2 -4 H2 O
25300 s h , 23800 s h , 1 5 7 0 0 , 13900 sh
N i( N O 3) 2 -GH2O
2 5 8 0 0 , 22200 s h , 18900 s h , 1 5 9 0 0 , 14200
The n i t r a t e b a n d s a re i d e n t i c a l to th e fre e io n b a n d s , in d i c a t i n g t h a t
n i t r a t e io n s a re n o t c o o r d i n a t e d . The lig a n d b a n d s a re s i m i l a r to th e
s p e c t r a o f t e t r a k i s c o b a lt(II) a n d z in c(II) n i t r a t e c o m p le x e s w h ic h w e re
d i s c u s s e d e a r l i e r , s u g g e s t i n g t h a t th e n a p h th y r id in e s a r e c h e la te d to
th e n i c k e l a to m .
C o m p a ris o n o f th e d i f f u s e - r e f l e c t a n c e s p e c tru m o f the*
N i(N N )2 (N O 3) 2 • 4 H2O c o m p le x w ith t h a t o f N i(N O 3) 2 ' 6 HgO (T able XIX)
s u g g e s t s t h a t th e g e o m e try of th e n ic k e l(II) io n is o c t a h e d r a l . From th e
in f r a r e d s p e c tru m i t i s n o t p o s s i b l e to d e c i d e w h e th e r tw o o r four w a te r
m o le c u le s a re c o o r d in a te d to th e n i c k e l a to m . But s i n c e th e n a p h th y r id in e s a re c h e l a t e d to th e c e n t r a l m e t a l , i t s e e m s l i k e l y t h a t th e re are
tw o c o o r d in a te d w a t e r m o le c u le s a n d tw o c h e l a t e d n a p h th y r id in e s in an
77
o c t a h e d r a l a r r a n g e m e n t.
C o o rd in a tio n o f four w a te r m o le c u le s to g iv e a
d o d e c a h e d r a l g e o m e try c a n n o t be ru le d o u t.
M n t N N ^ t N O g ^ a n d C u f N N ^ f N O g ^ : — The lig a n d b a n d s in th e
in f r a r e d s p e c t r a o f t h e s e tw o c o m p o u n d s a r e s u p e r im p o s a b le on t e t r a k i s
n i t r a t e c o m p l e x e s , w h ic h s u g g e s t s c h e l a t i o n o f th e n a p h th y r id in e m o le ­
c u l e s to th e m e ta l i o n s . H o w e v e r th e n i t r a t e io n b a n d s a re s im ila r to
t h o s e r e p o rte d for b i d e n t a t e n i t r a t e io n s (4 9 ,5 7 ). W h en fre e n itr a te i o n ,
sy m m e try
to C 0
, c o o r d in a te s to th e c e n t r a l m e ta l i t s sy m m e try i s lo w e re d
( c o v a l e n t l y b o u n d th ro u g h o n e o r tw o o x y g e n s ) .
C o tto n e t a l .
(44) h a v e re p o rte d th e in fr a r e d b a n d s for s e v e r a l n i t r a t e c o m p le x e s c o n ­
t a in in g n i t r a t e c o o r d in a te d th ro u g h tw o o x y g e n a to m s .
G a te h o u s e e t a l .
(58) h a v e s t u d i e d n i t r a t e c o m p le x e s in w h ic h th e n i t r a t e io n s a re c o ­
v a l e n t l y .b o n d e d th ro u g h o n e o x y g e n ato m a n d h a v e a s s i g n e d th e in f r a ­
re d a c t i v e b a n d s for th e n i t r a t e a n io n . T hey h a v e a l s o r e p o r te d th e
fo llo w in g a s s i g n m e n t s (T able XX) for d if f e r e n t r a n g e s o f o b s e r v a b le
m o d es in c o o r d in a te d n i t r a t e s .
T ab le XX
Bands (cm ^)
A s s ig n m e n ts
1 5 3 1 -1 4 8 1
a s y m m e tr ic s t r e t c h
1 2 9 0 -1 2 5 3
NOg sy m m e tric s t r e t c h
1 0 3 4 -9 7 0
NO s tr e tp h
8 0 0 -7 8 1
n o n p la n a r ro ck
78
The s tro n g n itr o g e n - o x y g e n s t r e t c h i n g b a n d a p p e a r in g in th e
r a n g e 1 0 3 4 -9 7 0 cm ^ w ill b e o b s e r v e d a s a w e a k b a n d fo r u n c o o rd in a te d
n i t r a t e a n io n . The n i t r a t e io n b a n d s o f s e v e r a l c o m p le x e s c o n ta in in g
f r e e , m o n o d e n t a t e , a n d b i d e n t a t e n i t r a t e io n s are l i s t e d in Table XXI for
c o m p a r is o n . The s tro n g b a n d a t 1035 cm ^ a n d 1018 cm ^ in th e m a n g a n e s e ( I l) a n d c o p p er(Il) c o m p l e x e s , r e s p e c t i v e l y , is i n d i c a t i v e of
c o o r d in a te d n i t r a t e io n s (Figure 11). This b a n d is. o b s e r v e d a s a w e a k
b a n d in t e t r a k i s n i t r a t e c o m p le x e s .
T ab le XXI
INFRARED ABSORPTION BANDS OF SOME NITRATE COMPLEXES (CM™1)
Io n ic n itr a te :
[C o (N H 3) 6 1(N O 3) 3
1 3 7 6 s , 1299 s h , 1045 w , 823 s
M o n o d e n ta te n itr a te :
[C o (N H 3) 4 (N O 3) 2 ]
. 1499 s , 1393 s , 1348 s h , 1266 s , 1049 w ,
1 0 1 0 s , 825 in, 800 w
[N i(P E t3) 2(N O 3) 2 ]
1513 m , 1418 s h , 1359 v s , 1272 s , 1 0 1 8 s
805 m
B id e n ta te n itr a te :
[( (C H 3)2P O )2 C o ( N 0 3) 2 ]„
1 5 1 7 s , 1492 s , 1469 s , 1317 s h , 1304 s h ,
1 2 8 2 s , 1 0 2 4 m , 812 w
[C o( ( C 6H 5) 3P 0 ) 2 ( N 0 3) 2 ]
1503 s h
1497 s , b r, 1493 s , 1290 s ,
1024 m , 812 w , 808 w
79
.C u lC gH A I0 , , I N O ,),
if— I—j_
-L- ioo
Cu ( C J L N J 0 ( NO, )
i - - 40 v
F ig u re 11.
In frared S p e c tra of C u (C g H g N 2) 2 Jg (N O 3) 2 a n d
C u ( C 8 H 6N 2) 2 (N O 3) 2 .
80
The C u(N N )7(N O 3) 2 c o m p le x h a d n o t b e e n p re p a re d a t th e tim e
th e r e f l e c t a n c e s p e c t r a w e re o b ta in e d a n d no c o m p a r is o n o f th e s p e c t r a
c a n be m a d e . The s o lu tio n s p e c t r a o f b o th C u(N N )2(N O 3) 2 and
C u(N N )2 ^g (N O 3) 2 c o m p le x e s in a b s o l u t e m e th a n o l s h o w a n a b s o r p tio n
-I
-I
b a n d a t 13000 cm r a th e r th a n th e 15900 cm o b ta in e d for th e l a t t e r
c o m p o u n d from i t s r e f l e c t a n c e s p e c t r a . This i n d i c a t e s t h a t th e m o le c u ­
l a r s t r u c t u r e s o f th e copper(II) c o m p o u n d s a re d iff e r e n t in th e c r y s ta l
a n d in s o lu tio n ; th e r e f o r e th e s o lu tio n s p e c t r a l d a ta c a n n o t be u s e d for
d ra w in g a n y c o n c l u s i o n s a b o u t th e g e o m e try o f th e c o p p e r atom in th e
so lid .
The s i m ila r ity o f th e lig a n d in fr a r e d b a n d s to t h o s e o b s e r v e d in
a ll t e t r a k i s c o m p le x e s a n d th e e v id e n c e for b id e n ta te c o o r d in a tio n o f
n i t r a t e io n s a r g u e s for th e m ore fa m ilia r d o d e c a h e d r a l g e o m e try . Two
n a p h th y r id in e m o le c u le s a r e r e p la c e d in t h e s e c a s e s by n i t r a t e i o n s .
C o(N N )2 (N O 3) 2 : -
C o m p a ris o n o f th e C o(N N )2 (N O 3) 2 in frared
s p e c tru m w ith th e o th e r n i t r a t e c o m p o u n d s d i s c u s s e d e a r l i e r in th is
s e c t i o n i n d i c a t e s t h a t n a p h th y r id in e s a re a g a in c o o r d in a te d through
b o th n itr o g e n s to th e c o b a l t a to m . H o w e v e r, th e n i t r a t e io n b a n d s a re
s i m i l a r to n i t r a t e c o m p le x e s (59) h a v in g m o n o d e n ta te c o o r d in a tio n .
This s u g g e s t s th a t c o b a lt(II) io n i s s u rro u n d e d by four n itr o g e n s from
n a p h th y r id in e a n d tw o o x y g e n s from n i t r a t e i o n s .
The d if f u s e r e f l e c t a n c e s p e c tru m o f t h i s c o m p le x (T ab le XIX)
d iff e r s from th e s p e c tru m o f th e C o ( N N ^ N O 3) 2 ’ 6 H2 O , in w h ic h o n ly
n a p h th y r id in e s a re c h e l a t e d to th e c o b a l t a t o m , b u t is s i m i l a r to t h a t o f
81
th e o c t a h e d r a l [(C H g )^ PO I 2 C o(N O g) 2 c o m p le x s t u d i e d b y C o tto n e t a l .
(5 9 ). The a b s o r p tio n b a n d s fo r th e p h o s p h in e o x id e c o m p le x h a v e b e e n
-I
r e p o r te d a t 20600, 19000, a n d 17920 cm . The v i s i b l e a b s o r p tio n b a n d s
o f th e Co(NKOgNOg)2
c o m p le x l i s t e d in T ab le XX a re v e r y s im ila r , s u g ­
g e s t i n g a s i m i l a r g e o m e try to t h a t o f th e p h o s p h in e o x id e c o m p le x .
From th e in fr a r e d a b s o r p tio n s p e c tru m i t w a s c o n c lu d e d t h a t th e n a p h th y r i d in e s w e re c h e l a t e d to th e c o b a l t atom a n d th e n i t r a t e io n s w e re
c o o r d in a te d th ro u g h o n e o f th e o x y g e n a t o m s . This w ill s u p p ly s i x c o ­
o r d in a tio n g ro u p s for th e c o b a lt(II) i o n , a n d a g e o m e try s im ila r to t h a t
o f th e p h o s p h in e o x id e c o m p le x .
C u(N N )2 Ig (N O g )2 =-
This c o m p le x h a s a n u n u s u a l s to ic h io m e tr y
w h ic h r e q u ir e s som e e x p l a n a t i o n . O ne m ig h t r e a s o n a b l y s u p p o s e t h a t
th e r e w e re in f a c t o n ly tw o n a p h th y r id in e m o le c u le s p e r c o p p e r a n d t h a t
s m a ll e rro rs in th e a n a l y s e s w e re r e s p o n s i b l e for th e d e r i v a t i o n s . H ow ­
e v e r , t h i s co m p o u n d h a s p r o p e r tie s d if f e r e n t from a s e c o n d com pound
( d i s c u s s e d ab o v e) w ith e x a c t l y tw o n a p h th y r id in e m o le c u le s p e r c o p p e r ,
a n d th e a n a l y s e s fo r a ll c o m p o n e n ts ( c o p p e r , c a r b o n , h y d r o g e n , a n d
an io n ) fit v e ry p r e c i s e l y th e re p o rte d f o r m u la , w h ic h g iv e s u s a m e a s u re
o f c o n f id e n c e in th e c h o s e n fo rm u la . The m a g n e tic m om ent o f th e co m ­
p le x (1.98 B . M . ) s u g g e s t s t h a t th e C u (N N )2 ^g(N O g)2 i s m o n o n u c le a r.
The lig a n d in f r a r e d b a n d s (T able XVIII a n d Figure 11) a re s im ila r to a ll
th e o th e r n i t r a t e s th u s fa r d i s c u s s e d i n d i c a t i n g b i d e n t a t e c o o rd in a tio n
o f th e n a p h t h y r i d i n e s . The n i t r a t e io n b a n d s are s im ila r to free n itr a te
82
io n s (F ig u re 11) w h ic h s u g g e s t s t h a t n i t r a t e io n s a re n o t c o o r d in a te d to
th e c o p p er(II) io n .
The d i f f u s e - r e f l e c t a n c e s p e c tru m o f Cu(NN)^ ^g (N O g )2 i s d iff e r­
e n t from t h a t o f th e C u (N N )^ (C 1 0 ^ )2 c o m p le x w h ic h s u g g e s t s th a t th e
g e o m e try o f th e copper(II) io n i s d if f e r e n t from t h a t o f th e p e r c h lo r a te
c o m p o u n d , w h ic h is in g o o d a g r e e m e n t w ith th e in fr a r e d d a t a .
The a b ­
s o rp tio n m axim a a re s im ila r to th o s e o f d i s t o r t e d o c t a h e d r a l copper(II)
c o m p le x e s r e p o r te d in t h e lit e r a t u r e (46) ( s e e Table X), b u t th e
c o p p er(II) e l e c t r o n i c a b s o r p tio n b a n d s a re s o b ro a d t h a t no c e r ta in c o n ­
c l u s i o n a s to th e g e o m e try o f th is c o m p le x c a n be d ra w n .
A g (N N ) N O g :-
The in fr a r e d s p e c tru m o f th e Ag(NN)NOg com pound
s h o w s s i g n i f i c a n t d i f f e r e n c e s from t h o s e n i t r a t e c o m p le x e s o f fir s t
tra n sitio n s e r ie s .
The s p l i t t i n g o f th e lig a n d b a n d a t 1128 cm * is n o t
o b s e r v e d in A g(N N )N O g, a n d s p l i t t i n g o f th e lig a n d b a n d s in th e re g io n
9 0 0 - 7 5 0 cm * i s q u ite d if f e r e n t from th e c o m p le x e s in w h ic h c h e la tio n o f
th e lig a n d h a s b e e n p o s t u l a t e d . The s p e c tr u m o f th e s ilv e r(I) com ­
p o u n d s o f b o th n i t r a t e p e r c h l o r a t e s a re v e r y s im ila r to t h a t o f
C u (N N )2 C l 2 in w h ic h n a p h th y r id in e s w e re c o o r d in a te d th ro u g h one o f
th e n itr o g e n s to th e copper(II) io n . The in fr a r e d b a n d s for th e n itr a te
a n io n s h o w th e u s u a l c h a r a c t e r i s t i c s o f t h e fre e io n s p e c tru m in d ic a tin g
t h a t n i t r a t e io n i s n o t c o o r d in a te d to t h e s ilv e r(l) io n . The in fra re d
s p e c tru m th u s s u g g e s t s m o n o d e n ta te c o o rd in a tio n for th e lig a n d in
83
Ag(NN)NOg c o m p le x w ith n i t r a t e io n n o t c o o rd in a te d to th e s i l v e r
a to m .
The u l t r a v i o l e t a b s o r p tio n b a n d s o f th e n i t r a t e c o m p o u n d s in
a b s o l u t e m e th a n o l s o l u t i o n s a n d t h e i r m o la r a b s o r p t i v i t i e s a re re p o rte d
in T ab le XXlL The p o s i t i o n s o f th e c o o r d in a te d lig a n d b a n d s do no t
c h a n g e s i g n i f i c a n t l y from t h o s e o f fre e lig a n d b a n d s , a lth o u g h th e re a re
som e e x tr a s h o u ld e r s o b s e r v e d a f t e r c p m p l e x a t i o n . The s h a p e s and
p o s i t i o n s o f th e b a n d s a re s i m i l a r to th e c o rre s p o n d in g p e r c h lo r a te
b a n d s l i s t e d in T a b le X.
SUMMARY OF PART III
The c o m p le x e s C o(N N )4 (N O 3) 2 0S H 2O a n d Zn(NN)4 (N O 3) 2 0S H 2O
have been sy n th esiz ed .
The d a ta i n d i c a t e a g e o m etry s i m i l a r to th a t o f
th e t e t r a k i s p e r c h lo r a te c o m p l e x e s .
Bis c o m p le x e s o f m a n g a n e s e (II), c o b a lt(II), a n d c o p p er(Il) w ith
s to ic h io m e t r y M (N N )2 (N O 3) 2 h a v e b e e n i s o l a t e d .
A n a ly sis o f th e d a ta
i n d i c a t e s t h a t th e n a p h th y r id in e s a re c h e l a t e d in a l l t h e s e c o m p le x e s ;
n i t r a t e io n s are c h e l a t e d to m a n g a n e s e (II) a n d co p p er(II), b u t m o n o d e n t a t e l y c o o r d in a te d in th e c o b alt(II) c o m p le x . D o d e c a h e d r a l g eo m etry
h a s b e e n s u g g e s t e d for th e m a n g a n e s e (II) a n d copper(II) co m p o u n d s a n d
o c t a h e d r a l g e o m e try for th e c o b a lt(II) c o m p le x .
84
T ab le XXII
U LTR A V IO LET A B S O R P T IO N SPEC TR A *
Cl)
X, n m
m ax
M n(N N )2 (N O 3)
, M
1K
X, nm
v, kK
£
m ax
, M
2
C o ( N N ) 2<N ° 3 > 2 ' ^ H g O
32.4
10600
309
32.4
11450
(303)
(33 .0 )
10600
(303)
(33.0)
10930
301
3 3. 2
11200
301
33.2
12030
(296)
(33.8)
9910
(296)
(33.8)
10500
(290)
(34 .5 )
7660
(290)
(34.5)
8150
(283)
(35.3)
5300
(284)
(35.2)
5850
257
3 8. 9
8100
258
38.8
C o(N N )
2
10200
CO
C o(N N )2(N O 3)
O
309
* 6 H 2O
309
3 2 .4
6400
309
3 2 .4
15100
(304)
(32.9)
6150
(304)
(32.9)
14500
302
33. 1
6800
301
33.2
15850
(296)
(33.8)
5950
(296)
(33.8)
13850
(290)
(3 4 .5 )
4500
' (290)
(34 .5 )
10800
(284)
(35 .2 )
3400
(284)
(35 .2 )
10150
258
38.8
4800
259
38.6
11150
85
T a b le XXII (c o n tin u e d )
X, nm
V, kK
X, nm
w
m
~
v, kK
1 k
Cu(NN)2 1 6 (N O 3) 2
e
max
,M 1
C u(N N )2 (NC)3 h
309
32.4
13050
309
32.4
11300
301
33.2
13650
301
33.2
11900
(297)
(33.7)
12 300
(297)
(33.7)
10800
(290)
(34.5)
9600
(290)
(34.5)
8650
(284)
(35.2)
7500
(284)
(35.2)
6750
(274)
(36.5)
7600
(274)
(36.5)
6750
(268).
(37.3)
9250
. (268)
(37.3)
8100
(264)
(37.9)
10300
(264)
(37.9)
9050
259
38.6
10600
254
39.4
10400
Zn(NN) ^(NOg)
Ag(NN)NO3
2 ' 6H2°
309
32.4
24000
309
32.4
6200
301
33.2
25150
301
33.2
6450
(297)
■ (33.7)
22100
(297)
(33.7)
5800
(290)
(34.5)
15900
(290)
(34.5)
4400
(284)
(35.2)
11900
(285)
(35.1)
3620
(273)
(3 6.6)
11700
(277)
(36.1)
3400
(271)
(36.9)
13150
(273)
(36.6)
3900
259
38.6
17650
260
38.5
5050
* P a re n th e se s re p re se n t sh o u ld ers.
86
The co m pound C u(N N )2 ^g(N O 3) 2 w a s p r e p a r e d from a q u e o u s s o l u ­
tio n a n d th e d a ta i n d i c a t e t h a t th e n a p h th y r id in e s a re c h e l a t e d to th e
c o p p e r a to m . No c e r t a i n a s s i g n m e n t o f s tr u c tu r e c a n b e m ad e in th is
case.
The c o m p le x N i(N N )2 (N O 3) 3 ’ 4 H2O h a s b e e n s y n t h e s i z e d . The
d a t a s u g g e s t c h e l a t i o n o f th e l i g a n d s w ith w a t e r m o le c u le s c o o r d in a te d .
O c ta h e d r a l or d o d e c a h e d r a l g e o m e try for th e n ic k e l(II) io n a re p o s s i b l e
e x p l a n a t i o n s o f th e d a t a .
E x p e rim e n ts w ith s ilv e r(I) io n r e s u l t e d in i s o l a t i o n o f an
Ag(NN)NO3 c o m p le x in w h ic h th e n a p h th y r id in e i s c o o r d in a te d m o n o d e n t a t e l y to th e s i l v e r a to m . The g e o m e try o f th e c o o r d in a tio n c o m p le x
is not know n.
87
PART IV. COPPER(I) COMPLEXES
In 19 70 s e v e r a l t r i s c o m p le x e s o f 2/7 - d i m e t h y l - l /8 - n a p h th y r id in e
w ith v a r io u s m e ta ls o f g e n e r a l form ula M ( d m N N ^ C l O ^ g , in c lu d in g a
brow n co p p er(II) c o m p o u n d , w e re r e p o r te d (7). The a n a l y s i s p r e s e n te d
in th a t re p o rt i n d i c a t e d t h a t a ll c o m p le x e s c o n ta i n e d o c t a h e d r a l l y c o ­
o r d in a te d b i d e n t a t e n a p h t h y r i d i n e . C opper(II) c o m p o u n d s in w h ich th e
m e ta l atom i s s u rro u n d e d b y s i x n itr o g e n a to m s a re n o rm a lly b l u e , a n d
th e r e p o r t o f a brow n c o p p er(II) c o m p le x s o c o o r d in a te d w a s th u s r a th e r
u n u s u a l . A ttem p ts to d u p l i c a t e th e s y n t h e s i s o f t h i s brow n m a te ria l
w ith ' b o th NN a n d dmNN w e re m a d e . The d e s i r e d c o m p o u n d s w e re o b ­
ta i n e d b u t c a n n o t be c h a r a c t e r i z e d a s copper(II) c o m p o u n d s . The tw o
p r o d u c ts w e re a n a l y z e d a n d c h a r a c t e r i z e d . M a g n e tic m o m e n ts and
e l e c t r o n i c s p e c t r a i n d i c a t e d t h a t b o th c o m p o u n d s w e re copper(I) co m ­
p le x es.
M o re o v e r, for c o m p a r is o n , co p p er(I) c h lo rid e c o m p le x e s of
n a p h th y r id in e s w e re p r e p a r e d d i r e c t l y from copper(I) c h lo r id e and
n a p h th y rid in e s.
Four co p p er(I) c o m p le x e s o f 1 ,8 -n a p h th y rid in e a n d i t s 2,7-dim ethyl
d e r iv a tiv e c o n ta i n in g c h lo r id e a n d p e r c h lo r a te a n io n s h a v e b e e n s y n ­
t h e s i z e d a n d c h a r a c e r i z e d in th is r e s e a r c h . The a n a l y t i c a l a n d p h y s i c a l
d a ta a re g iv e n in T ab le V. C o n d u c tiv ity m e a s u re m e n ts o n th e copper(I)
n a p h th y r id in e c o m p le x e s in a c e t o n i t r i l e , n i t r o m e t h a n e , o r a b s o lu t e
m e th a n o l i n d i c a t e t h a t th e c o m p le x e s in s o lu tio n a re io n ic ; th e v a lu e
88
o b ta in e d c o r r e s p o n d s to s i n g l y io n iz in g s a l t s , w h ic h a g r e e s w ith r e ­
s u l t s r e p o r te d e a r l i e r fo r co p p er(l) c o m p le x e s (6).
M a g n e tic s u s c e p t i b i l i t y m e a s u r e m e n ts bn th e c o m p le x e s by th e
G ouy m e th o d i n d i c a t e t h a t th e c o m p le x e s a re d ia m a g n e tic . V isib le a n d
u l t r a v i o l e t s p e c t r a s h o w o n ly c h a r g e t r a n s f e r b a n d s a s s o c i a b l e w ith th e
lig a n d .
T h e s e tw o o b s e r v a t i o n s c l e a r l y e s t a b l i s h th e form al o x id a tio n
s t a t e o f th e m e ta l in t h e s e c o m p le x e s a s + 1 . The c o m p le x CUg(NN)Clg
g a v e a r e p r o d u c ib le m e ltin g p o in t a t 292 ± .1 ° C . All o th e r c o m p o u n d s in
t h i s g ro u p d e c o m p o s e d w ith o u t m e ltin g a t te m p e r a tu r e s a t o r b e lo w
270°C .
The in fr a r e d s p e c t r a o f th e co p p er(I) co m p o u n d s a re su m m a riz e d
in T ab le XXIII. A s s ig n m e n ts for th e lig a n d b a n d s' a re g iv e n in th e
l i t e r a t u r e (37).
Cu(NN) ClO^: — The in f r a r e d s p e c tru m o f th is c o m p le x w a s co m ­
p a r e d w ith t h o s e o f c o m p le x e s d i s c u s s e d e a r l i e r in t h i s t h e s i s .
The
lig a n d b a n d s are s i m i l a r to C u(N N )C lg a n d Cu(NN)Brg s p e c t r a in w h ic h
n a p h th y r id in e s a re b e l i e v e d to b rid g e a c r o s s two c o p p e r(ll) i o n s . This
s u g g e s t s a s im ila r s tr u c tu r e fo r th e c o p p er(I) co m p o u n d . The b r o a d ,
-I
-I
v e ry s tro n g p e r c h l o r a t e b a n d s a t 1115 cm - a n d 1087 cm ( a n tis y m m e tric
s tr e tc h ) a n d th e b a n d s a t 635(m) cm ^ a n d 622(s) cm * (a n tis y m m e tric
bend) a re c h a r a c t e r i s t i c o f c o o r d in a te d p e r c h lo r a te (2 6 ), W h en p e r ­
c h l o r a t e io n c o o r d i n a t e s i t s sy m m e try i s lo w e re d from T^ (fre e ion) to
Cg
( c o o r d in a tio n th ro u g h o n e ox y g en ) o r Cgv ( c o o r d in a tio n th ro u g h tw o
T ab le XXIII*
SELECTED INFRARED ABSORPTIONS (4 0 0 0 -2 5 0 CM X) OF COPPER(I) COMPLEXES
Band
NN
Cu(NN)ClO4
C u 2(N N )C l2
Band
dmNN
I
1555 v s
1563 m
1565 s
I '
1532 s
1555 m
1540 w
II
1492 v s
1507 v s
1502 v s
II
1505 v s
1517 v s
1517 v s
III
1465 s
1486 v s
1460 w
III
1360 w
1372 s
1375 m
IV
1395 s
1402 m
1388 m
IV
1240 m
1252 vw
1253 v w
V
1228 s
1238 v s
12 66 v w
V
1206 w
1218 m
1211 w
VI
•
1148 v s , b r
•
VI
•
1087 v s , b r
VII
1128 v s
•
1135 w
VII
847 v s
' 855 v s
866 v s
VIII
•
•
•
•
1115 v s , b r
«
»
«
O
VIII
805 v s
810 w
812 m
IX
•
•
•
•
1087 v s , b r
■
0
•
•
IX
778 v s
798 v s
788 v s
X
1027 s
1040 s , b r
1042 m
X
•
a
775 w
776 m
650 v w
O •
•
•
•
■
•
•
•
•
•
•
•
•
Cu(dm N N )2 C104
C u 2(dmNN) C D
XI
835 v s
853 m
835 v s
XI
622 m
648 w
XII
808 v s
840 s
795 vw
XII
.
#
618 s
773 m, s h
825 w
790 s , s h
XIII
442 m
457 w
450 vw
XIV
343 m
350 w
348 v w
XIII
XIV
XV
XVI
XVII
XVIII
XIX
•
•
•
•
758 v s
600 w
537 m
797 v s , s h
792 v s
635 m
622 s
542 w
•
•
•
,
770 w, sh
637 w
«
•
•
538 v w
* The a s s i g n m e n t s are: s, stro n g ; v s , v e ry s tro n g ; m, medium; w, w eak ; vw, v e ry w eak;
s h , s h o u ld e r; br, b r o a d .
90
U
15
18
I i-T r ir
C u ( C m H m N0 )0 C I O , -I-—
■■?—
Figure 12.
i
In frared S p e c tra o f C
C u ( C g H 6N 2)ClO4 .
u
(
^ClO^ and
20
25
30
WO ^
91
o x y g e n s ) . E a c h o f th e tw o in fr a r e d a c t i v e b a n d s is s p l i t in to two com ­
p o n e n ts in Cgv sy m m e try a n d in to th re e c o m p o n e n ts in
sym m etry
(8,2 6 ,6 0 ). The fre e p e r c h l o r a t e b a n d s a t a b o u t 1100 cm * a n d 620 cm ^
s p l i t in to tw o b a n d s r e s u l t i n g in four b a n d s a s o b s e r v e d in t h i s com ­
pou n d (F igure 12). T h e s e b a n d s i n d i c a t e t h a t th e p e r c h l o r a t e ion is c o ­
o r d in a te d th ro u g h o n e o f th e o x y g e n a to m s to th e c o p p e r atom ( s e e
Figure 12). The Cu(NN)ClO^ i s p ro b a b ly a p o l y n u c le a r c o m p le x w ith
n a p h th y r id in e m o le c u le s b rid g e d a c r o s s tw o c o p p e r a to m s a n d p e r c h lo r ­
a t e s c o o r d in a te d th ro u g h o n e o f th e o x y g e n s to th e c o p p e r(l) i o n s . The
b i n u c l e a r s tr u c tu r e sh o w n in Fig u re 13 i s s u g g e s t e d for t h i s c o m p le x . A
v e r y s i m i l a r c o p p er(l) c o m p le x o f d ia z o a m in o b e n z e n e h a s b e e n p r e v i­
o u s l y r e p o r te d (31).
OClOg
F ig u re 13.
S u g g e s te d s tr u c tu r e for Cu(NN)ClO^ c o m p le x .
CufdmN N jgClO g a n d C u g W m N N jC lg :— The in fr a r e d s p e c t r a of
c o p p er(l) c o m p le x e s w ith 2 ,7 - d i m e t h y l - l , 8 - n a p h t h y r i d i n e a r e l i s t e d in
T ab le XXIII. The s h i f t s o f th e lig a n d b a n d s upon c o o r d in a tio n are
92
s i m i l a r in b o th Cu(CimNN)2 ClC^ a n d C u 2 (^ m N N )G l2 c o m p o u n d s . The
s p l i t t i n g o f th e fre e lig a n d b a n d a t 1128 cm * i s n o t o b s e r v e d in th e
s p e c tru m o f th e C u 2 (d m N N )C l2 . This re g io n o f th e s p e c tr u m in
C u(dm N N )2 C10g is c o v e r e d b y p e r c h lo r a te io n b a n d s a n d th e lig a n d
b a n d s a re n o t o b s e r v a b l e . Three v e r y s tro n g b a n d s w h ic h o c c u r a t 847,
-I
805, a n d 778 cm in th e free lig a n d s p e c tru m a re o b s e r v e d a s two v e ry
s tro n g a n d tw o m edium a n d w e a k b a n d s a f t e r c o o r d in a tio n .
The p e r ­
c h lo r a te a n io n b a n d s in C u(dm N N )2 C10^ o c c u r a s a b ro a d b a n d a t
1087(vs) cm "*■ a n d a s h a r p s i n g le b a n d a t 6 1 8(s) cm \ i n d i c a t i v e of
i o n ic p e r c h lo r a te (7,54) (Figure 12). The lig a n d b a n d s in copper(l) c o m ­
p l e x e s o f dmNN a re s i m i l a r to th o s e o f C u(dm N N )2X2 (X= C l or Br) in
w h ic h m o n o d e n ta te c o o r d in a tio n to th e c o p p e r a to m s w a s s u g g e s t e d .
The c o p p e r - c h l o r i n e s t r e t c h i n g freq u e n cy , w a s n o t o b s e r v e d in th e s p e c ­
trum o f C u 2 (d m N N )C l2 .
The u l t r a v i o l e t a b s o r p tio n b a n d s o f Cu(dm N N )2 C10^ a re s im ila r in
s h a p e to th o s e o f dmNN c o m p le x e s o f copper(II) i o n , b u t d iff e r e n t from
th e o th e r co p p er(I) c o m p le x e s in t h i s s t u d y . There i s g e n e r a l l y a s h a rp
i n c r e a s e in i n t e n s i t y o f th e u l t r a v i o l e t s p e c tru m o f th e copper(I) com ­
p o u n d s , b u t in th is co m p o u n d no s u c h i n c r e a s e i s o b s e r v e d . This s i m i ­
l a r i t y o f th e u l t r a v i o l e t a b s o r p tio n to t h a t o f m o n o n u c le a r copper(II)
c o m p o u n d s a n d th e d i f f e r e n c e s from o t h e r c o p p er(l) c o m p o u n d s s u g g e s t s
a v e ry d if f e r e n t s tr u c tu r e for t h i s c o m p le x .
93
In th e C u(dm N N )2 C104 c o m p le x t h e n a p h th y r id in e s a r e co o rd in a ted
th ro u g h o n e o f th e n itr o g e n s a n d th e p e r c h lo r a te a n io n e x i s t s a s an
i o n ic s p e c i e s .
The s to ic h io m e t r y o f C u(dm N N )2 C10^ c o m p le x i s i d e n t i ­
c a l to th e C u (M p y )2 ClO4 a n d C u (P h e n )2 ClO4 c o m p o u n d s (6), bu t c o o r d i­
n a tio n m u s t be v e r y d if f e r e n t in th e dmNN c o m p le x i f th e lig a n d is
m o n o d e n ta te a s i n d i c a t e d in th e in fr a r e d s p e c tr u m . Thus th e d a ta a v a i l ­
a b le a re i n s u f f i c i e n t to d e te r m in e th e c o o r d in a te g e o m e try o f th e c o p p e r
in C u(dm N N )2 C104 . The e a r l i e r w o rk e rs (7) h a v e a s s i g n e d a b id e n ta te
c o o r d in a tio n for t h i s s a m e c o m p le x , e r r o n e o u s l y r e p o rte d a s
C u (dm N N )g(C lO ^ )2 ; h o w e v e r th e p o s i t i o n s a n d i n t e n s i t i e s o f th e b a n d s
in th e r e g io n 9 0 0 - 7 0 0 Cm * do n o t c o r r e s p o n d to th e b a n d s l i s t e d for th e
r e s t o f th e tr i s c o m p o u n d s . This w ork s u g g e s t s t h a t dmNN i s c o o rd i­
n a t e d m o n o d e n ta te ly a n d th e p e r c h l o r a t e i s i o n i c , b u t i s n o t s u f f ic ie n t
to i n d i c a t e a c o o r d in a te g e o m e try fo r th e c o p p er(l) io n .
C o m p a ris o n o f th e in fr a r e d s p e c tru m o f C u 2 (d m N N )C l2 w ith th o s e
o f C u(dm N N )2 C l 2 a n d C u(dm N N )2 Br2 in w h ic h m o n o d e n ta te n a p h th y r id in e c o o r d in a tio n i s h y p o t h e s i z e d s h o w s t h a t th e s p e c t r a a re v ery
s i m i l a r . This s u g g e s t s t h a t th e dmNN lig a n d in t h i s c o m p o u n d is a l s o
m o n o d e n ta te .
C u 2 (N N )C l2 : -
The in fr a r e d s p e c tru m o f th e C u 2 (N N )C l2 is s i m i ­
l a r to t h a t o f C u(N N )2 C l2 in w h ic h n a p h th y r id in e s are c o o r d in a te d
th ro u g h o n e of th e n itr o g e n s to th e c o p p e r a to m . The s i n g l e b a n d a t
113 6(s) cm ^ in th e c o p p er(Il) c o m p le x a p p e a r s a t 1 135(w) cm ^ in th e
94
co p p er(I) c o m p o u n d . The v e r y s tro n g 835 cm * fre e lig a n d b a n d o c c u r s
_1
w ith o u t a n y s h i f t a s a s i n g l e s h a rp b a n d a n d th e lig a n d b a n d a t 760 cm
—i
a p p e a r s a s a w e a k s h o u ld e r a t 770 cm a f t e r c o m p l e x a t i o n . This i n d i ­
c a t e s t h a t n a p h th y r id in e i s c o o r d in a te d th ro u g h o n e o f th e n itr o g e n s to
th e c o p p er(I) io n a s o c c u r s in th e C u C N N ^ C ^ c o m p le x . No b a n d s a re
o b s e r v e d in th e re g io n 3 5 0 -2 5 0 cm * w h ic h can be a s s i g n e d to th e
c o p p e r - c h l o r i n e s t r e t c h i n g f r e q u e n c y . The c o p p e r - c h l o r i n e s t r e tc h i n g
f r e q u e n c y o f C u 21(C H g N = N C H g )C l9 h a s b e e n re p o rte d a s a w e ak b a n d a t
311 cm * (2 8 ). The w e a k n e s s o f th is b a n d m ay a c c o u n t for th e fa ilu re to
fin d i t in th e s p e c tru m o f C U g (N N )C l^. The sh a rp m e ltin g p o in t o f th e
c o m p le x a t 292 ± 1 °C s u g g e s t s t h a t th e c o m p le x i s m o le c u la r and h e n c e
t h a t th e c h lo r in e a to m s a re c o o r d in a te d to th e c o p p er(l) io n .
M o le c u la r w e ig h t d e te r m in a tio n s w o u ld be v e ry v a l u a b l e bu t th e
lo w s o l u b i l i t y o f th e c o m p o u n d s d id n o t p e rm it m o le c u la r w e ig h t
m easu re m e n ts.
The u l t r a v i o l e t s p e c t r a o f a l l th e c o m p l e x e s , a p a r t from th e
C u td m N N lg C lO ^ , w e re s i m i l a r in s h a p e , b u t d iffe re d from th o s e qf
co p p er(II) c o m p o u n d s d i s c u s s e d e a r l i e r . There w a s a s h a r p i n c r e a s e in
i n t e n s i t y o f th e s p e c tru m w ith s e v e r a l s h o u ld e r s a b o v e 36000 cm . The
b a n d a t a b o u t 38000 cm * p r e s e n t in co p p er(II) c o m p le x e s (T able VII)
d o e s n o t a p p e a r in th e C U g(N N )C lg, C U g(dm N N )C lg, a n d Cu(NN)ClO^
c o m p le x e s (T ab le XXIV), b u t s i n c e no a s s i g n m e n t o f t h i s b a n d h a s b e e n
m ad e th e s i g n i f i c a n c e o f t h i s a b s e n c e i s u n c l e a r .
95
Table XXIV
ULTRAVIOLET ABSORPTION SPECTRA*
X,nm
v, kK
X, nm
w
m
"
1 k
v - kK
em a x ' M ~
C u 2(N N )C l2
Cu(N N )ClO 4
307
32.6
5650
308
32.5
5750
300
3 3. 3
6000
(302)
(33.1)
5750
(295)
(33.9)
5300
.301
33. 2
6100
(289)
(34.6)
4100
(295)
(33.9)
5500
(283)
(35.3)
3100
(288)
(34.7)
4200
(284)
(35.2)
3300
Cu(dmNN) , C l O 4
C u 2 MmNN) C I2
315
31.8
19480
315
31.8
10500
307
32.6
17300
307
32.6
9000
302
33.1
17000
302
3 3. 1
8800
(297)
(33.7)
12800
(296)
(33.8)
6100
(290)
(34.5)
10200
(290)
(34.5)
4700
(285)
(35.1)
8600
(283)
(35.3)
3200
250
40.0
11500
* P a re n th e se s re p re se n t s h o u ld e rs .
96
The s im ila r s to ic h io m e t r y o f C u ^(N N )C lg a n d Cug(dm N N )C lg s u g ­
g e s t s so m e r e la tio n b e tw e e n t h e s e s t r u c t u r e s . D ia z e n e c o m p le x e s w ith
th e g e n e r a l form ula (RN=NR)CUgClg h a v e b e e n s tu d ie d p r e v io u s ly (2 8 ).
An X -ra y c r y s t a l l o g r a p h i c s tu d y o f a r e p r e s e n t a t i v e c o m p o u n d ,
(CH gN =N CH g)CU gClg h a s sh o w n (30) t h a t th e c o m p le x c o n s i s t s o f i n ­
f in ite c h a in s of c o p p e r a n d c h lo r in e a to m s (F igure 14). H o w ev e r th e
m e ltin g p o in t o f th e C u 7 (NN)Clg s u g g e s t s t h a t it i s m o le c u la r and
h e n c e a n in f i n ite M - C l - M b rid g e d l a t t i c e s e e m s u n lik e ly .
M o re o v e r a s tr u c tu r e s im ila r to th e d i a z i n e s i s n o t p o s s i b l e for
n a p h th y r id in e c o m p o u n d s . N a p h th y rid in e i s a f la t rig id m o le c u le and
c o o r d in a tio n to tw o a d j a c e n t c h a i n s o f C u C l w ith n a p h th y r id in e s ly in g
in b e tw e e n th e c h a i n s r e q u ir e s th e s t e r i c a l l y im p o s s i b l e r o ta tio n of o n e
o f th e n itr o g e n a to m s 1 8 0 ° a ro u n d th e C=C o f th e rin g . The in fra re d
s p e c t r a o f th e c o m p o u n d s do n o t i n d i c a t e a n y b rid g in g p r o p e r tie s for
lig a n d s.
- Cu—
— Cu
Figure 14.
---- -CH
S tru c tu re o f (C H gN =N C H g)C ugC lg co m p o u n d .
97
A s tr u c tu r e r a t h e r d if f e r e n t from t h a t o f th e d i a z e n e i s r e q u ir e d ,
b u t th e r e is no c l e a r i n d i c a t i o n in th e d a ta a s to th e n a tu r e o f th is
s t r u c t u r e . This p ro b lem c l e a r l y m e rits fu rth e r s tu d y .
SUMMARY OF PART IV.
Two c o p p er(I) c o m p le x e s o f 1 ,8 - n a p h th y r id i n e , Cu(NN)ClO^ a n d
C u g (N N )C lg , h a v e b e e n s y n t h e s i z e d .
From c o m p a r is o n s o f th e d a ta
w ith t h o s e c o m p le x e s d i s c u s s e d e a r lie r , a b rid g e d n a p h th y r id in e c o o r d i­
n a tio n a c r o s s th e two co p p er(l) io n s in Cu(NN)ClO^ w ith p e r c h lo r a te io n
b e in g c o o r d in a te d m o n o d e n ta te ly to th e c o p p e r atom w a s fo u n d . In
CUg(NN)Clg c o m p le x , m o n o d e n ta te d c o o rd in a tio n o f th e lig a n d w a s s u g ­
g e s t e d a n d a p o s s i b l e s t r u c t u r a l g e o m e try w a s d i s c u s s e d .
S im ila r ly , tw o copper(I) c o m p le x e s o f 2 ,7 - d im e th y l- 1 ,8 n a p h th y r id in e , Cu(dm N N )gC104 a n d Cug(dm N N )Clg w e re i s o l a t e d .
M o n o d e n ta te c o o r d in a tio n for th e li g a n d s w a s a s s i g n e d , a m o n o n u c le a r
s p e c i e s for Cu(dm N N )gClC^ a n d p o ly n u c le a r a rra n g e m e n ts for
CUg(dmNN)Clg a re s u g g e s t e d .
A P P E N D IX
99
SULFATE AND ACETATE COMPLEXES
S e v e ra l s u l f a t e a n d a c e t a t e c o m p o u n d s o f t r a n s i t i o n m e ta l io n s
w ith 1 ,8 -n a p h th y rid in e h a v e b e e n s y n t h e s i z e d .
The d a ta on t h e s e co m ­
p l e x e s h a v e n o t b e e n a n a l y z e d , b u t th e a n a l y t i c a l a n d p h y s i c a l d a ta
a re g iv e n in T a b le s XXV a n d XXVI r e s p e c t i v e l y .
SULFATE COMPLEXES:
Cu(NN)SO4 - 4 FI2O a n d Cu(NN)SO4 *2 H2O : - To a s o lu tio n of
0.125 g (0.5 mmol) o f CuSO4 *5 H2O in 10 ml o f w a te r 0.09 I g (0.7 mmol) o f
NN w a s a d d e d in a P e tri d i s h . This b lu e s o lu tio n w a s k e p t in a c lo s e d
c h a m b e r c o n ta i n in g a c e t o n e . U pon d iff u s in g a c e to n e in to th e s o lu tio n
for 24 h o u rs th re e d if f e r e n t k in d s o f c r y s t a l s w e re o b t a i n e d .
w h ic h w e re g re e n a n d b l u i s h - g r e e n w e re a i r s t a b l e .
Two forms
They w e re c o l l e c t ­
ed m a n u a lly on a f i l te r p a p e r a n d w e re a i r d r i e d . The a n a l y s e s of t h e s e
tw o forms w h ic h w e re s e p a r a t e d m a n u a lly s h o w e d th a t t h e y had the
s a m e s to ic h io m e t r y . The th ird fo rm , tu r q u o i s e b l u e , w a s n o t a ir s t a b l e
a n d form ed a l i g h t b lu e p o w d e r a t room t e m p e r a t u r e . T h e s e la th -fo rm
u n s t a b l e c r y s t a l s w e re s e p a r a t e d on a f i l t e r p a p e r a n d w e re a n a ly z e d
i m m e d ia te ly , b e fo re d e c o m p o s itio n Could ta k e p l a c e . The a n a l y s i s
s h o w e d t h a t th is u n s t a b l e co m pound c o n ta i n e d four m o le c u le s of h y d r a ­
tio n w a t e r , b u t th e p o w d e r o b ta in e d a f t e r l o s s o f w a te r c o n ta i n e d o n ly
tw o m o le c u le s o f w a t e r . The w e ig h t l o s s in th e c o m p o u n d , w h ic h w a s
100
d e te r m in e d by w e ig h in g th e c r y s t a l s b e fo re a n d a f t e r d e c o m p o s itio n ,
w a s c o n s i s t e n t w ith t h e s e d e t e r m i n a t i o n s .
C u(N N )2SO4 : -
To a s o lu tio n o f 0.2 5 g (Im m o l) o f CuSO4 ' 5 H2O in
40 ml o f d im e th y lfo rm a m id e w a s a d d e d 3 -5 d ro p s o f c o n c e n t r a t e d H2 SO4
fo llo w e d b y a d d itio n o f 0.26 g (2 mmol) o f N N . The s o lu tio n w a s r e ­
flu x e d for s e v e r a l m i n u t e s .
This s o lu tio n w a s f il te r e d from th e p r e c i p i ­
t a t e , if a n y , a n d th e v o lu m e o f th e f i l t r a t e w a s r e d u c e d to a b o u t 20 ml
b y k e e p in g th e s o lu tio n w arm a n d u n d e r r e d u c e d p r e s s u r e . The c o n c e n ­
t r a t e d s o lu tio n w a s k e p t a t room te m p e r a tu r e u n til c r y s t a l l i z a t i o n w a s
c o m p le te d . The t u r q u o i s e - b l u e p r e c i p i t a t e w a s f il te r e d a n d r e c r y s t a l ­
l i z e d from d im e th y lfo rm a m id e . The c r y s t a l s w ere w a s h e d w ith
chloroform fo llo w e d b y a c e t o n e a n d d rie d o v e r c a lc iu m c h l o r i d e .
Co(NN)SO4 1S H2O , Ni(NN)SO4 - 4 H2O , a n d Zn(NN)SO4 • 4 H2O: A s o lu tio n o f 0.2 81 g ( I mmol) o f CoSO4 ' 7 H2O , or 0.2 63 g (I mmol) o f
NiSO4 • 6 H2O , a n d / o r 0.2 87 g ( I mmol) o f ZnSO4 17 H2O in 10 ml of w a te r
c o n ta i n in g 0.13 g ( I mmol) o f NN w a s d iff u s e d by a c e t o n e for 2 4 h o u r s .
The n e e d le - f o r m c r y s t a l s o f g r e e n i s h - b l u e n i c k e l , p in k c o b a l t , and
w h ite z in c c o m p le x e s w e re i s o l a t e d .
The c r y s t a l s w e re c o l l e c t e d by
f i l t r a t i o n , w a s h e d w ith c h lo ro fo r m , a n d a ir d rie d . T h e s e com pounds
w e re r e c r y s t a l l i z e d from t h e i r a q u e o u s s o lu tio n s by a s im ila r m e th o d .
Mn(NN)SO4 15 H2O : -
A s o lu tio n o f 0.169 g (Im m o l) o f
MnSO4 ’ H 2O a n d 0.2 g (1.54 mmol) o f NN in 15 ml o f w a t e r w a s k e p t in an
i c e - b a t h for a fe w h o u rs u n til a w h ite p r e c i p i t a t e w a s o b t a i n e d . This
101
p r e c i p i t a t e w a s c o l l e c t e d b y f i l tr a tio n a n d w a s r e c r y s t a l l i z e d from i t s
a q u e o u s s o lu tio n by th e s a m e p r o c e d u r e . The w h ite n e e d l e s w ere c o l ­
l e c t e d on a f i l te r p a p e r , w a s h e d w ith c h lo ro fo r m , a n d a i r d r ie d .
Cu(NN)SO^ ° H g O ' CHgOH: — To a s o lu tio n o f 0.2 5 g (Im m o l) o f
CuSQg *5 HgO in 10 ml o f w a t e r 0.13 g ( I mmol) o f NN w a s a d d e d fo llo w e d
b y a d d itio n o f 30 ml o f a b s o l u t e m e th a n o l o r m e th a n o l-c h lo ro fo rm m ix ­
tu re (3 ;1 ). U pon s ta n d i n g for 30 m in u te s th e b lu e c r y s t a l s w e re c o l l e c t ­
e d in a s i n t e r e d g l a s s f u n n e l, w a s h e d w ith a b s o lu t e m e th a n o l, and a ir
d rie d .
Ag2(N N )g SO4: -
To a s o lu tio n o f 0.155 g (0.5 mmol) o f Ag2SO4 in
70 ml o f h o t w a t e r 0.13 g (I mmol) o f NN in 10 ml o f warm w a t e r w a s
a d d e d . The s o lu tio n w a s c o o le d s lo w ly u n til c r y s t a l l i z a t i o n w a s co m ­
p le te d .
The w h ite n e e d le - f o r m c r y s t a l s w e re c o l l e c t e d b y f il t r a t i o n ,
w a s h e d w ith w a te r fo llo w e d by a c e t o n e , a n d d rie d o v e r c a lc iu m c h lo r ­
id e .
The r e c r y s t a l l i z a t i o n of th e com p o u n d w a s p e rfo rm ed from hot
w a te r .
ACETATE COMPLEXES:
N i(N N )2 (OAc)2 *4 H g O : - A s o lu tio n o f 0.245 g (Im m o l) of
n ic k e l(Il) a c e t a t e t e tr a h y d r a te in 10 ml o f w a te r c o n ta in in g 0.2 6 g (2 mmol)
o f NN w a s k e p t a t room te m p e ra tu re to d e c r e a s e th e v o lu m e o f th e s o l u ­
tio n to a minimum b y s lo w e v a p o r a tio n .
The c l e a r g re e n s o lu tio n w a s
k e p t in a c h a m b e r c o n ta i n in g e i t h e r a c e t o n e o r a c e t o n e - e t h y l a c e t a t e
102
m i x t u r e . A fter d if f u s io n fo r 2 4 -7 2 h o u r s , g re e n w e ll- f o r m e d c r y s t a l s
w e re c o l l e c t e d m a n u a l ly , w a s h e d w ith c h lo ro fo rm , a n d d rie d o v er
c a lc iu m c h lo r id e . The c o m p le x w a s r e c r y s t a l l i z e d b y th e s a m e p ro ­
cedure.
C o tN N ^ fO A c jg *4 H g O : - An a q u e o u s s o lu tio n o f 0.249 g (Im m o l)
o f Co(OAc)g ' 4 HgO a n d 0.2 6 g (2 mmol) o f NN in 10 ml o f w a t e r w a s p r e ­
p a r e d . D ark p in k c r y s t a l s w e re o b ta in e d by s lo w e v a p o r a tio n of th e
s o lu tio n a t room t e m p e r a t u r e . The w e ll- f o r m e d c r y s t a l s w e re c o l l e c t e d
m a n u a lly on f i l t e r p a p e r a n d a i r d r ie d . T h e s e c r y s t a l s w e re p u rifie d by
r e c r y s t a l l i z a t i o n from a q u e o u s s o l u t i o n .
C u (N N )2 (OAc ) 2 : ~
To a s o lu tio n o f 0.4 g (2 mmol) o f
Cu(OAc)2 • HgO in 30 ml o f warm DMF 0.52 g (4 mmol) o f NN w a s a d d e d .
This s o lu tio n w a s k e p t in a d e s i c c a t o r c o n ta in in g c o n c e n t r a t e d HgSO^
u n d e r r e d u c e d p r e s s u r e for a few d a y s . The t u r q u o i s e - b l u e c r y s t a l s
w e re f il te r e d in a s i n t e r e d g l a s s f u n n e l, w a s h e d w ith a b s o l u t e e t h a n o l ,
a n d d rie d o v e r c a lc iu m c h lo r id e .
Cu(N N )(O A c)2 '2 HgO: — An a q u e o u s s o lu tio n o f 0.199 g (Im m o l)
o f Cu(O A c)2 *HgO a n d 0.13 g (Im m o l) o f NN in 10 ml o f w a t e r in a s m a ll
P e tri d i s h w a s k e p t p a r t i a l l y c o v e r e d a t room te m p e r a t u r e . The blue
c r y s t a l s w e re f i l t e r e d , w a s h e d w ith 95% e t h a n o l , a n d a i r d r ie d .
Table XV
SULFATE COMPLEXES
% C alcd . -
t
C
H
Ma
t
AD
” - ' • % Found
C
17.64
H
M
C o lo r
C o n d u c t.
A
A (molar)
.
cm 2 mho
Cu(NN)SO4 M H 2O
17.56 26.55
Cu(NN)SO4 M H2O
29.54 3.09 19.50 29.49
29.81 2.87 19.42 29.35 Blue-^green
6
C u(N N )2 SO4
45.79 2.88 15.13 22.88
44.88 3.01 14.96 22.94 T u rq u o ise
7
17.64 26.32 T urquoise
*. .
Co(NN)SO4 -S H2O
15.71 25.60
15.63 25.50 Pink
3
Ni(NN)SO4 -4 H2O
16.45 26.91
16.26 27.07 G reen
3
Mn(NN)SO4 -S H2O
14.80 25.88
14.94 25.91 W h ite
9
Ag 2 (N N ) 2 SO4
37.71 16.79
37.56 16.83 W h ite
53
a M = m e ta l. ^ A - a n io n . c The c o n d u c t i v i t i e s w e re m e a s u re d in a b s o l u t e m e th a n o l.
103
Cu(NN)2SO4 • H2O *CH3OH 43.44 3.86 13.52 20.44 43.52 3.75 13.5.5 2 0.23 Blue
“' '
T ab le XXVI
ACETATE COMPLEXES
% C a lc d .-
(
C
H
Ma
-% Found
X r
Ab
C
H
M
C o lo r
A
C o n d u c t .C C o n c n .
a (molar)
M x lO 4
cm^ mho
18.27 33.95
18.41 34.14 Blue
20
7.42
47.57 5.14 11.24 22.69 B row nish- - ' 54
o ra n g e
7.18
C o(N N )2(OAc)
i-H
Cu(NN)(OAc)2 Z H 2O
CD
7.69
N
21
TP
14.25 26.88 Blue
O
tcT
14.38 2 6.75
TP
C u(N N )2 (OAc)
5.15 11.17 22.39
47.17 5.36 11.36 2 1 4 0 G reen
a M = m e t a l . ^ A= a n io n . c The c o n d u c t i v i t i e s w e re o b ta in e d in a b s o l u t e m e th a n o l s o l u t i o n s .
104
N i(N N )2(OAc)2 •4 H 2O 47.18 5.15 11.53 23.19
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