Complexes of a-pyridone with divalent transition metals
by Clifford Carlton Houk
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 Clifford Carlton Houk (1966)
Abstract:
Six new compounds of α-pyridone (C5H5NO) have been prepared. Single crystal x-ray diffraction
analysis has shown one of these compounds, CuC12.C5H5NO, to be a chlorine bridged dimer. X-ray
powder diffraction data show that three of these compounds, MnC12 • 1C5H5NO, NiC12 • 1C5H5NO
and CoC12 • 1C5H5NO are isomorphous and appear to have structures similar to CuC12 • 1C5H5NO.
Magnetic moment, solid and solution spectrophotometric data collectively indicate that all four
compounds probably have a distorted tetrahedral configuration in the solid state. C0C12 • 3 C5H5NO
has been prepared; magnetic, solid and solution spectrophotometric data support an octahedral structure
for this compound. The sixth compound, CuCl2 • 2 C5H5NO has not been assigned a specific
structure;, the data for this compound are inconclusive COMPLEXES OF a - PYRIDO NE WITH
DIVALENT TRANSITION METALS
by
CLIFFORD CARLTON HOUK
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 lf illm e n t o f th e re q u ir e m e n ts for th e d e g r e e
of
DOCTOR OF PHILOSOPHY
in
C h e m is tr y
A pproved:
H e a d V M a jo r D e p a rtm e n t
------
C h a ir m a n , E x am in in g C o m m itte e
D e a n , G ra d u a te D iv is io n
MONTANA STATE UNIVERSITY
B o zem an , M o n tan a
J u n e , 1966
ill
ACKNOWLEDGEMENT
The a u th o r w i s h e s to e x p r e s s h i s s i n c e r e a p p r e c i a t i o n for th e a d v ic e ,
e v e r p r e s e n t e n c o u r a g e m e n t , a n d c o n tin o u s s tre a m of i d e a s g iv e n by' Dr„
K e n n eth E m erso n d u rin g th e c o u r s e of t h i s s tu d y a n d w ritin g o f th e t h e s i s „
A p p r e c ia tio n i s e x p r e s s e d to th e D e p a rtm e n t of C h e m is tr y for a
g r a d u a te t e a c h i n g a s s i s t a n t s h i p a n d t h e D e p a rtm e n t o f H e a l t h , E d u c a tio n
a n d W e lf a r e for a n N. D 0E. A. f e llo w s h ip w h ic h m ade g r a d u a te s tu d y p o s s i b l e .
To D rs. R. J. O 'C o n n o r, W illia m B. C o o k , a n d K. J. G o e rin g for th e i r
e n c o u r a g e m e n t, g u id a n c e , a n d w i l l i n g n e s s to l i s t e n d u rin g th e a u t h o r 's
te n u r e a t M o n ta n a S ta te U n iv e rs ity .
To my p a r e n ts , w h o s e g u id a n c e , f a i t h a n d f o r e s i g h t e d n e s s d e v e lo p e d
th e n e c e s s a r y fo u n d a tio n u p o n w h ic h th e b u ild in g b lo c k s o f life c o u ld be
sec u re ly p la c e d .
F in a lly , to my w ife, E v e ly n , a n d c h i l d r e n , M e l i s s a a n d S c o tt, w ith o u t
w h o s e c o n f id e n c e a n d e n c o u r a g e m e n t n o n e o f t h i s w o u ld h a v e b e e n u n d e r­
tak en .
iv
TABLE OF CONTENTS
Page
Vita ..........................
ii
A c k n o w l e d g e m e n t .......................................
iii
T a b le of C o n t e n t s ............. ................................... ...................... ................. ...
iv
L i s t o f T a b l e s .................................................................................. ................................ ... .
vi
L is t of F i g u r e s .......................................................
A b s t r a c t .................................................................
v iii
xi
I n t r o d u c t i o n ..............................................................
I
A n a ly tic a l T e c h n i q u e s .............................................. . .............................. ...................
11
E x p e rim e n ta l P r o c e d u r e s a n d R e s u lts .................................................
14
P u r if ic a t io n of <X -pyridone.....................................................................
14
P r e p a r a tio n o f A nhydrous M e t a l (II) C h l o r i d e s ....................... ...
14
S o lv e n t P u r i t y ................................................................................................................
17
S y n t h e s i s o f D ic h lo ro -m o n o -O L -p y rid o n e M e ta l (II) C o m p l e x e s . . . .
18
S y n t h e s i s o f .D ic h lo r 6 - n - 0t- p y r id o n e M e ta l (II) C o m p l e x e s ................
33
D iscu ssio n
................................. ... i . . . . .
................................. ................................
41
D i c h l o r o - mo n o - a - p y rid o n e M e ta l (II) C o m p le x e s . . . . . . . . . . . .
D ic h lo ro -m o n o -d X '-p y rid o n e C o p p e r ( I I ) .................' .................................
D ic h lo r o - m o n o - o .- p y r id o n e C o b a lt(II)
.... .................
D ic h lo r o - m o n o - o —p y rid o n e N ic k e l(II) . ...............................
D i c h l o r o - mo n o -c x -p y rid o n e M a n g a n e s e (II ) . .................................... .
41
47
50
57
59
D i c h l o r o - n - CX-p y rid o n e M e ta l (II) C o m p l e x e s ..............................................
■D i c h l o r o - b i s - o t - p y r i d o n e C o p p e r ( I I ) ................................
D ic h lo r o - tr is - c x - p y r id o n e C o b a l t ( I I ) ........................................................
■ I• S u m m a r y ...................
62
63
64
67
V
T a b le o f C o n te n ts
(C o n tin u e d )
Page
A p p en d ix A .................................... ... . ..............................................................................
69
: E x p e rim e n ta l P r o c e d u r e s a n d R e s u lts ' .............................................. ...
P u r if ic a tio n of A c e ta m id e ........................................................................ ... .
P r e p a r a tio n a n d I d e n t i f i c a t i o n o f Sodium A ceta m id e . . . . . . . .
70
70
71
A tte m p te d -S y n th e s e s of B is a c e ta m id o C opper(II) C o m p le x e s . . . . .
• D ir e c t C o m b in a tio n ...........................................................................................
S o x h le t E x tr a c tio n T e c h n i q u e s ....................................................................
I n te r n a l H y d r o l y s i s ...........................................................................................
C l o s e d S y ste m A ttem p ts . . . . . . . . . . . . . . . . . . . . . . . . . .
73
73
77
78
79
A tte m p te d S y n t h e s i s of B is ^ c e ta m id o N ic k el(II) C o m p l e x ....................
80
A tte m p te d S y n t h e s i s o f B isb e n z a m id o C opper(II) C o m p le x
81
. . . . . .
D i s c u s s i o n .................................................
L ite r a tu r e C ite d
............................................................................................................ ... .
^ 82
90
LIST OF, TABLES
Table No.
I.
T itle
Page
Cu(II) tiompounds with Subnormal M agnetic M oments . . . . . . .
II. . C u(II) Compounds with Normal M agnetic Moments . . ....
. ■
. - '• v '■
'
III,
. U ltraviolet Spectral Bands for CL-pyridqne . . .. . . . .
2
8
. v 17
. 19
IV.
MCI2 • I C 5H5NO Elem ental A n alyses . . . . . . . ,. . . . . . .
V.
MCI2 * I CgH5 NO M agnetic S u sc e p tib ilitie s arid Moments
VI.
MCI2 • I CgHgNO Powder D iffraction Data . . . . . . . . . .
VII.
M Cl2 • I CgH5NO U ltraviolet Absorption Bands and Molar
A b so rp tiv ities.
............. ...
. .. .
VIII.
M Cl2 • I C 5H5NO V isib le Absorption Bands and Molar
AbsOrptiVities ............................. .................................................. ... >
27
M Cl2 • I C 5HgNO M olecular W eight D eterm inations . ■...■
32
C uCl2 • 2 C 5H5NO and C oC l2 - S C 5H5NO Elem ental
A n alyses ......................
33
C uCl2 • 2 C 5H 5NQ1and C oC l2 - 3 C 5H5NO Powder D iffraction
Data ...................
34
IX.
X.
XI.
*
.-I
20
.
XII.
CuCl2 • 2 C 5H 5NO and C oC l2 - 3C 5H5NO U ltraviolet
S p ectal Bands ...................................................................................................... 34
XIII.
CuCl2 - 2 C 5H 5NO and C oC l2 • S C 5H5NO V isib le Spectral
B a n d s ................... ... . . , . . . . . . . . ................ ...................................... .• 37
XIV.
C uCl2 • 2 C 5H5NO and C oC l2 • 3 CgH5NO M agnetic Sus­
c e p tib ilitie s and Moments ................., .........................
XV.
XVI .
40
Infrared Band A ssignm ents MCl^ • I C 5H5NO C o m p le x e s ............42
V isib le Spectral Bapds of Known Chlorine-Bridged Cu(II)
C o m p o u n d s .........................................................................................
49
Room Temperaturq M agnetic M oments for Co(II) Compounds . . .
51
XVIII • V isib le Solution Spectra Bands for Kiiown Co(II) Compounds . . .
53
XVII.
v ii
L i s t of T a b le s
T a b le No.
XIX.
XX.
(C o n tin u e d )
' T itle
Page
D if f u s e R e f le c ta n c e Bands of Known Co(II) C o m p o u n d s
. . . . . . . . . . .
57
In f ra r e d B ands fo r C uC lg * 2 C 5H 5NO a n d C oC lg ° 3 C 5H 5NO . . .
63
Sodium Acetamide- A n a ly s e s ........................................................ ...
73
- XXIII.
Sodium A c eta m id e S o lu b i litie s . . . . . . . . . . . . . . . . . . . . . . .
73
XXIV.
S o lv e n ts U s e d in A tte m p te d -S y n th e s e s . . . . . . . . . . . . . . . . . .
74
-XXV.
R e s u lts o f S e l e c t e d B is a c e ta m id o C opper(II) • I S o lv e n t
S y n t h e s i s ................................. ... ....................
75
C l o s e d S y ste m R e s u lts . . . . . . . . . . . . . . . . . . . . . . . . . . .
80
S u s p e c t e d R e a c tio n P r o d u c t s ............. ...
82
■XXI.
■XXII.
XXVI.
XXVII.
M a g n e tic M o m e n ts o f Known N i (II) C om pounds
.................55
v iii
LIST OF FIGURES
F ig u re
No.
I . C u C l2 • I C 5H 5 NO S tru c tu re
T itle
Page
..................................................................................
3
2 . C u (C H 3C O O )2 • I H 2O S t r u c t u r e ............. ...................... : ....................................... 5
3 . O b s e r v e d C a r b o x y la t e B id e n ta te B in u c le a r C o n f ig u r a tio n s
4 . C u (H C O O ) 2 - 4 H 2O S tru c tu re
. .................
6
.............................................. ...
7
5 . C a r b o x y la te a n d A c e ta m id o Group S im ila r ity ..................................................
9
6 . P o s s i b l e B id e n ta te L i g a n d s .....................................................................................
9
7. In fra re d S p ectru m o f O L -p y rid o n e........................................................................... 14
8 . U l tr a v io le t S p e c tru m o f Ct-pyridone in H 2Q". ................................. ... . . . . 15
9 . U ltr a v io le t S p e c tru m o f od-pyridone in C 2H 5OH ............................................... 1>5
10. U ltr a v io le t S p e c tru m o f a - p y rid o n e in C H 2C N ............. ...
16
1 1 . U l tr a v io le t S p e c tru m o f CXrp y rid o n e in HCONCCH-g^ . . . . . . . . . . .
16
1 2 . V is ib le A b s o rp tio n Spectru m of C u C lg " I C 5H 5NO in H 2O
22
. . . . . . .
13. V is ib le A b so rp tio n S p ectru m of C u O l2 • I C 5H 5NO in G 2 H 5OH
. ; , .
?2.
1 4 . V is ib le A b so rp tio n S p ectru m of C u C l2 • I C 5H 5 NO in C H 3C N ..... 23
15. V is ib le A b so rp tio n Spectru m of C o C l 2 • I C 5H 5NO in H 2O
....................
23
1 6 . V is ib le A b so rp tio n Spectru m o f C 0 C I2 • I C 5H 5NO in C 2 H 5OH . . . . .
24
•17.
V is ib le A b so rp tio n Spectrupn of C o C lg • I C 5H 5NO in C H 2C N
. . . .
24
•18. V is ib le A b so rp tio n Spectru m of N iC l2 • I C 5H 5NO in P 2O . .■................
25
19. V is ib le A b so rp tio n Speptrum of N iC l2 • I C 5H 5NO in C 2H 5OH . . . . .
25
2 0 . V is ib le A b so rp tio n S p ectru m of N iC l2 • I C 5H 5NO in H C O N (C H 2)2 . . 26
ix.
L i s t of F ig u r e s
(C o n tin u e d )
F ig u re
No. <
T itle
Page
21 o D iff u s e R e f le c ta n c e S p e c tru m o f C u C lg • I C 5H 5-NO . .....................................28
22. D if f u s e R e f le c ta n c e
S p ectru m o f C 0 C I2,• I C gHgNO . ................................. 2 8
2 3 . D iff u s e R e f le c ta n c e S p ectru m of N iC lg • I C 5H 5N O ..................................29
2 4 . D iff u s e R e f le c ta n c e S p e c tru m o f M nC lg • I C 5H 5NO . . . . . . . . . . .
29
2 5 . In fra re d S p e c tru m of C u C lg • I CgH gNO
30
2 6 . In fra re d S p ectru m of C oC lg •I C gH gNO
....... ..............................
. . . » ....................................................31
2 7 . In fra re d S p ectru m of N iC lg • I C g H g N O .......................... ................................... 31
2 8 . In fra re d S p e c tru m o f M nC lg • I C 5H 5N O ..............................................
32
2 9 . Visible- A b so rp tio n Spectru m of C u C lg ■2 CgHgNO
in H g O . . . . . . . . .
35
3 0 . V is ib le Absorption- S p ectru m of C u C lg • 2 CgHgNO
in C H g C N ................ 35
3 1 . V is ib le A b s o rp tio n S p ectru m of C o C lg • 2 CgHgNO
in H g O . . . . . . . .
3 2 . V is ib le A b so rp tio n Spectru m of C o C l g • 2 CgHgNO in C gH gO H
3 3 . V is ib le A b so rp tio n S p ectru m of C o C lg ° 2 CgHgNO
. . . .
36
36
in C H g C N .................37
3 4 . D iff u s e R e f le c ta n c e S p ectru m o f C u C lg ■ 2 C g H g N O ....................................... 38
3 5 . D iff u s e R e f le c ta n c e S p ectru m of C o C lg •' 3 C g H g N O ...................................
38
3 6 . I n f ra r e d S p ectru m of C uC lg • 2 C g H g N O ...................
39
3 7 . In fra re d S p ectru m of C o C lg • 3 CgH gNO
40
3 8 . (X -pyridone (CgHgNO) S tru c tu re
..........................................................
................................. .......................................42
3 9 . U n it C e l l R e l a tio n s h ip B etw e e n C u C lg ? I CgHgNO a n d
C o C lg - I C 5H 5N O .................................... ................... : ................................ ...
45
X
,
L ist, o f . F ig u r e s . (C o n tin u ed )
F ig u re
No.
'40.
T itle
Page
C u C l2 • I C 5H 5NO S t r u c t u r e ........................................................................................ 46
4 1 . In fra re d S p e c tru m o f A c e ta m id e ......................
70
4 2 . In fra re d S p ectru m o f Sodium A c e t a m i d e ....................................................
72
4 3 . C u C l2 S t r u c t u r e .............................................. ................................................... . . . . 83
4 4 . V is ib le A b so rp tio n S p ectru m of Blue-^Grepn C r y s t a l s frgm
C u C l2 - N a C H 3C O N H - C 5H 5N S y s t e m ....................................................
84
4 5 . In fra re d S p e c tru m o f B lu e - G r e e n C r y s t a l s from
C u C l2 - N a C H 3C O N H - C 5H 5N S y s te m ................................
85
4 6 . In f ra r e d S p e c tru m o f B lu e -G re e p C r y s t a l s from
C u C l2 - C ^ H 5N Alone . . . . . . . . . . . .
, 86
4 7 . In f ra r e d .S p e c tru m o f P y rid in e . . . . . <! . .................... ...................... ... . . . . 86
■
x i'.
ABSTRACT
S ix n e w c o m p o u n d s o f a - p y r i d o n e (C gH ^N P) h a v e b e e n p r e p a r e d .
S in g le c r y s t a l x - r a y d if f r a c tio n a n a l y s i s h a s sh o w n o n e o f t h e ^ e doinp o u n d s,
C u C l2 • I C 5H 5NO, to b e a c h lo rin e bridgec} dim er. X - r a y p o w d e r d if f r a c tio n
d a ta sh o w that" th r e e o f t h e s e c o m p o u n d s, M n C l^ • IC g H ^ N O ,
N iC l2 • I C 5H 5NO a n d C 0 C I2 • I C 5H 5 NO a re is o m o rp h o u s a n d a p p e a r to
h a v e s t r u c t u r e s s im ila r to C u C l2 • I C 5H 5 N O . M a g n e tic m o m e n t, s o lid arid
s o lu tio n s p e c tr o p h o to m e tr ic d a ta c o l l e c t i v e l y i n d i c a t e t h a t a l l four c o m - ,
p o u n d s p ro b a b ly h a v e a d i s t o r t e d t e t r a h e d r a l c o n f ig u r a tio n in th e s o lid
s t a t e . C 0 C I2 • 3 C 5H 5NO h a s b e e n p r e p a re d ; m a g n e tic , s o lid a n d s o lu tio n
s p e c tr o p h o to m e tr ic d a t a s u p p o rt a n o c t a h e d r a l s tr u c tu r e for t h i s c o m p o u n d . '
The s ix th c o m p o u n d , C u C l 2 • 2 C ^ff^N O , h a s n o t b e e n a s s i g n e d a s p e c i f i c
s tru c tu re ;, th e d a ta for t h i s c o m p o u n d a re i n c o n g l u s i v e .
INTRODUCTION
The Cu(II) io n (3d^) n o rm a lly h a s tine u n p a ire d e l e c t r o n in th e 3d s u b - ,
s h e l l . Cu(II) h a s a c a l c u l a t e d s p in o n ly m a g n e tic m om ent o f 1.73 Bohr M a g ­
n e to n s (B.M.) r e g a r d l e s s o f th e b o n d t y p e . o f i t s c o m p o u n d s . A ctu ally , th e
o b s e r v e d v a l u e s of th e m a g n e tic m om ent a re L 9 to 2 . 2 . B.M. for m o s t Cu(II)...
c o m p o u n d s w ith io n ic or w e a k c o v a l e n t b o n d s a n d I. 72 to 1.82 B.M. for
c o m p o u n d s w ith s tro n g c o v a l e n t b o n d s ( I ) . Thus, Cu(II) c o m p o u n d s w ith
m a g n e tic m o m e n ts lo w e r th a n 1.73 B.M. a re u n u s u a l . S e v e r a l Cu(II) c o m - "
p o u n d s w ith u n u s u a l m a g n e tic m o m en ts h a v e b e e n p re p a re d a n d i n v e s t i g a t e d
(T ab le.I).
M a g n e tic m o m e n ts .are a m e a s u r e .of th e num ber o f 1Unjpaired e l e c t r o n s
p e r atom o r m o l e c u l e . P a r a m a g n e tic s u b s t a n c e s c o n ta i n o n e or more u n ­
p a ir e d e l e c t r o n s p e r atom or m o le c u le ; d ia m a g n e tic s u b s t a n c e s h a v e no u n ­
p a ir e d e l e c t r o n s . T h e re fo re , a s u b n o rm a l m a g n e tic m om ent m e a n s th e n u m - .
b e r of u n p a ir e d e l e c t r o n s p e r atom o r m o le c u le h a s d e c r e a s e d ; e l e c tr o n
i n t e r a c t i o n b e tw e e n u n p a ir e d d e l e c t r o n s o n c l o s e l y o r i e n t e d C u ,a to m s or
u n p a ir e d d e l e c t r o n s w ith e l e c t r o n s from th e lig a n d w ill d e c r e a s e th e n u m b er
o f u n p a ir e d e l e c t r o n s . T h e re fo re , Cu(II) c o m p o u n d s w ith u n u s u a l m a g n e tic .;
m o m en ts m u s t p ro v id e a p a th w a y t h a t p e rm its s u c h e l e c t r o n i n t e r a c t i o n .
I ‘
Two p o s s i b l e p a th w a y s for e l e c t r o n i n t e r a c t i o n h a v e b e e n p ro p o s e d ;
m e t a l - m e t a l i n t e r a c t i o n (bond fo rm atio n ) b y , d i r e c t o v e r la p o f d o r b it a ls on
c l o s e l y o r ie n te d C u a to m s a n d a s u p e r e x c h a n g e m e c h a n is m in v o lv in g C u d ■
o r b i t a l s a n d pTr o r per o r b i t a l s o f t h e l i g a n d . If th e f i r s t p a th w a y w e re c o r ­
r e c t , o n e w o u ld e x p e c t th e m a g n e tic m o m en t to be d e p e n d e n t u p o n th e
- 2 T a b le I
Cu(H) C o m p o u n d s w ith S u b n o rm al M a g n e tic M o m en ts
L ig an d
. Form ula .
B.M.,
M a g n e tic M o m e n t3
A c e ta te io n
C u (C H 3C O O )2 • I H 2O
1.43
A c e ta te io n
C u (C H 3C O O ) 3 - I C 5H 5 N
1.43
Fo rm ate io n
C u (H C O O ) 2 • 4 H 3O
1.64
B e n z o a te io n
C u ( C 6H 5C O O )3 • 4 H 20
1.40
P y rid in e -N -o x id e
C u C l3 • I C 5H 5 NO
0.85
P y rid in e -N -o x id e
C u C l3 - 2 C 5H 5NO
0.63
Q u in o l i n e - N - o x i d e
C u C l 3 • I C 9H 7NO
0.36
B u ty rate io n
C u ( C 3H 7C O O )3 • H 3O
1.35
O x a l a t e io n
C u (C O 2 C O 2 )
1.20
S u c c in a t e io n
C u [ C 0 2 (CH2 ) 2C O 2J 2 - 2 H 3O
1 .4 0
N , N , D im e th y la c e ta m id e
C u (C lO 4)2 • [C H 5C O N (C H 3)2J 4 • H 2O
1.57
T r ip h e n y l a r s in e o x id e
1 ,2 ,4 T riaz o le '
.C u B r2 - [(C6H 3 ) 3A sO j2
/
N -N '
\
CuSO4 / y
\
- 4 H 20
HC
.
CH
1.56
1.62
Vf /
a Room te m p e r a tu r e
d i s t a n c e b e t w e e n i n t e r a c t i n g Cu a to m s „ If th e r e w e re b o n d fo rm atio n b e ­
t w e e n Cu a to m s , i t w o u ld be o n e o f , t h r e e t y p e s : O '(d z^—d 'z ^ ) , Tr(dxz—d ' x z ,
d y z —d 'y z ) o r 6 (dxy—d 'x y , d x 2 - y 2 —d ' x 2 - y 2 ) . In a t e t r a g o n a l l y d i s t o r t e d
s y s te m (copper(II) a c e t a t e ) , TT b o n d s a r e n o t li k e l y b e c a u s e th e o r b it a ls in
- 3 q u e s t i o n a re l o w e s t in e n e r g y o f th e 3d o r b i t a l s . The d x ^ - y ^ l e v e l h a s th e
h i g h e s t en erg y , b u t o v e r la p b e tw e e n dz^ o r b i t a l s s h o u ld b e g r e a te r a n d
th e r e f o r e th e b o n d in g w ill be d e te r m in e d by c o m p e titio n b e tw e e n d z ^ (cr) a n d
dx2-y2(<5) o r b i t a l s . R o ss a n d Y a te s (2), R o ss (3) a n d R oyer (4) fav o r S bond
fo rm a tio n . F o r s te r a n d B a llh a u s e n (5) fa v o r cr bond f o r m a tio n . If a s u p e r
e x c h a n g e m e c h a n is m w e re c o r r e c t , o n e w o u ld e x p e c t th e m a g n e tic moment
to b e d e p e n d e n t u p o n th e e l e c t r o n d e n s i t y of th e p7T a n d per o r b i t a l s of th e
l i g a n d . S c h lu e tte r (6), K okozka (7,8) a n d H a n s e n a n d B a llh a u s e n (9) s t a t e
t h a t in t e r a c t i n g Cu a to m s a re o n ly w e a k ly c o u p le d by d o r b i t a l o v e rla p a n d
s u g g e s t a s u p e r e x c h a n g e p a th w a y i n s t e a d .
S u p er e x c h a n g e w a s a l s o fa v o re d in a s tu d y by H a tf ie ld a n d P a s c a l
(10) who s y n t h e s i z e d a n d i n v e s t i g a t e d h o m o lo g s of C u C lg " I C 5H 5NO
(C 5H 5NO i s p y r i d i n e - N - o x i d e ) . C u C lg • I C 5H 5NO h a s b e e n p re p a re d a n d
sh o w n to b e a n o x y g e n b rid g e d b i n u c l e a r (dim eric) c o m p o u n d , w ith th e
s tr u c tu r e sh o w n in F ig u re I, by Morrow, S c h a e f e r a n d Smith (11). The Cu
Cu
Cu
Cl
F ig u re I .
.Cl
0
C l.
O
*C1
C uC lg • I C 5H 5NO S tru ctu re
- 4 a to m s a n d b rid g in g o x y g e n a to m s lie in t h e s a m e p la n e ; th e d i s t a n c e b e - ,
t w e e n b rid g e C u a to m s is 3.23 + (0. O l-S ).'. The e n v iro n m e n t o f e a c h Cu atom
i s a d i s t o r t e d t e t r a h e d r o n . Some s t u d i e s l i s t i n g M -M d i s t a n c e s do h o t g iv e
s t a n d a r d d e v i a t i o n s ( u n c e r ta in tie s ) for b o n d l e n g t h s . M -M d i s t a n c e s t h a t
a p p e a r in t h e d i s c u s s i o n w ith o u t a c c o m p a n y in g u n c e r t a i n t i e s m ay v a ry a s
m uch a s - + 0 .1 S . T h is c o m p o u n d h a s a m a g n e tic m om ent of 0.85 B.M. a t
room te m p e r a t u r e . The 3.23 S d i s t a n c e b e tw e e n th e C u a to m s m a k e s d ir e c t
d o r b i t a l i n t e r a c t i o n l e s s l i k e l y a n d s u g g e s t s a s u p e r e x c h a n g e in e c h a n is m
m ig h t b e f u n c t i o n i n g . H a tf ie ld a n d P a s c a l h a v e s u b s t i t u t e d f u n c tio n a l
g ro u p s w ith d if f e r e n t e l e c t r o n w ith d ra w in g a n d e le c tr o n r e l e a s i n g p r o p e r tie s
in t h e fo u r p o s i t i o n o f p y r i d i n e - N - o x i d e . The new l ig a n d s w e re th e n u s e d to
p re p a re a s e r i e s of C u C l 2 • I R - C 5H 4NO c o m p o u n d s (R = s u b s t i t u t e d group)’.
T h ey a s s u m e d th e p r o d u c ts w e re i s o s t r u c t u r a l (oxygen b r id g e d d im ers) to
C u C lg • I C 5H 5N O . The m a g n e tic m o m e n ts of t h e i r c o m p o u n d s d e c r e a s e d a s
t h e e l e c t r o n r e l e a s i n g a b i l i t y of th e s u b s t i t u e n t i n c r e a s e d . The d e c r e a s e of
th e m a g n e tic m om ent i n d i c a t e d th e e l e c t r o n d e n s i t y in th e tt o r b it a ls o f th e
b rid g in g o x y g e n a to m s i n c r e a s e d a n d p e rm itte d i n c r e a s e d i n t e r a c t i o n b e ­
t w e e n t h e u n p a ir e d Cu d e l e c t r o n s a n d th e o x y g e n Tr e l e c t r o n s . They c o n ­
c lu d e d t h a t a s u p e r - e x c h a n g e m e c h a n is m w a s fa v o re d b e c a u s e th e am o u n t of
o v e r la p o f th e d o r b i t a l s s h o u ld no t b e a f f e c t e d by.ring, s u b s t i t u e n t s . M u to
a n d J o n a s s e n (12) h a v e u s e d mono, d i a n d t r i s u b s t i t u t e d p y r i d i n e - N - o x i d e s
to p re p a re c o p p e r (II) h a l i d e c o m p l e x e s . T h eir r e s u l t s co n firm th o s e of H a t ­
f ie ld a n d P a s c a l ; th e m a g n e tic m o m en ts of t h e c o m p o u n d s w e re d e p e n d e n t
- 5 u p o n th e e l e c t r o n r e l e a s i n g a b i l i t y o f th e s u b s t i t u t e n t . T hey p ro p o s e d tw o
p a th w a y s for s u p e r e x c h a n g e :
1.
c r p a th :
Sdcr(Cu)
* Sspcr^(O) t—> Sdc-(Cu)
2.
i r p a th :
SdTr(Cu)
» Sprr(O)
> Sdrr(Cu)
T h ey s u g g e s t e d th e a- p a th w a y w a s fa v o re d from th e d a ta o b t a i n e d .
O v e r la p o f Cu d o r b i t a l s a s a n e x p l a n a t i o n for th e s u b - n o r m a l m a g ­
n e tic m o m en ts o f som e Cu(II) c o m p o u n d s g a in e d s u p p o rt fo llo w in g th e d e t e r ­
m in a tio n o f th e s tr u c tu r e o f C u (C H g C O O )2 • I HgO by v a n N ie k irk and
S c h o e n in g (13). The s tr u c tu r e is sh o w n in Figure 2 . The d i s t a n c e b e tw e e n
CH3
F ig u re 2 .
C u (C H g C O O )2 • I H 3O S tru c tu re
b rid g e d Cu a to m s is 2.61 2 (14); th e d i s t a n c e b e tw e e n C u a to m s in C u m e ta l
i s 2 .5 6 ± 0.005 S . C u (C H 3C O O )3 • I H 3O (Figure 2) h a s a m a g n e tic m om ent
o f 1.43 B.M. a t room te m p e r a t u r e . The p ro x im ity of th e b r id g e d Cu a to m s
s u g g e s t e d e le c tr o n i n t e r a c t i o n b y o v e r la p o f d o r b it a ls from e a c h Cu a t o m .
- 6 —
The C u (C H g C O C )^ • I HgO r e s u l t s in d u c e d a d d itio n a l s t r u c t u r a l i n v e s t i g a ­
tio n of k n o w n Cu(II) c o m p o u n d s w ith u n u s u a l m a g n e tic m o m e n t s , p a r t i c u ­
la r ly t h o s e c o n ta i n in g th e c a r b o x y la te group (1 5 -2 1 ).
The c a r b o x y la te group m ay a c t a s a m o n o d e n ta te or b i d e n t a t e l i g a n d ,
i . e . , it m ay c o o r d in a te th ro u g h o n e or b o th o x y g e n a to m s . Known s t r u c tu r e s
o f Cu(II) c a r b o x y la te c o m p o u n d s w ith u n u s u a l m a g n e tic m o m en ts show th e
c a r b o x y la te group c o o r d in a te d a s a b i d e n t a t e lig a n d to tw o Cu ato m s (b in u c le a r) in th r e e d if f e r e n t c o n f ig u r a tio n s (Figure 3) (13, 18, 19).
R
R
1
C
M
O
M
M
syn-syn
Fig u re 3 .
M M-
O
0
sy n -a n ti
a n ti-a n ti
O b s e r v e d C a r b o x y la te B in u c le a r B id e n ta te C o n fig u ra tio n s
C u (C H g C O O )2 • I H 2O, th e re fo re , h a s a s y n - s y n b i n u c l e a r b id e n ta te c o n ­
f i g u r a t i o n . O th e r C u(Il) c a r b o x y la te c o m p o u n d s ( s tru c tu re unknow n) w ith
u n u s u a l m a g n e tic m o m en ts a re b e l i e v e d to be b in u c le a r b i d e n t a t e com ­
pounds .
C u (C H g C O O )2 • I C gH gN (p y rid in e) h a s b e e n p re p a re d a n d p ro v en i s o s t r u c t u r a l (d im e ric , s y n - s y n b id e n ta te , b rid g e d C u - C u d i s t a n c e 2 .64 +
0 ,0 0 6 %) to C u (C H 3C O O )2 • I H2O (2 0 ).
C u (C H 3C O O )2 • I C 5H 5N h a s a
m a g n e tic m om ent of 1.43 B.M . a t room t e m p e r a t u r e . A n o th er a c e t a t e ,
C r(C H 3C O O )2 • I H 2O is a l s o i s o s t r u c t u r a l (C r-C r d i s t a n c e 2 .6 4
2
)
to
- 7 C u (C H 3 CO O )2 • I H 2O; h o w e v er, C r(C H 3C O O )2 • I HgO i s d ia m a g n e tic a t
room te m p e r a tu r e (21). N orm ally, Cr(II) h a s four u n p a ire d e l e c t r o n s o c c u p y ­
in g d o r b i t a l s . The p ro x im ity o f th e m e ta l i o n s in t h e s e c o m p o u n d s a g a i n
s u g g e s t e d e l e c t r o n i n t e r a c t i o n th ro u g h o v e r la p of d o r b i t a l s o n n e ig h b o rin g
m e ta l a t o m s .
The c a r b o x y la te g ro u p h a s a l s o p ro v id e d in fo rm a tio n fa v o rin g a s u p e r
e x c h a n g e p a th w a y . C u (H C O O )2 • 4 H 2O h a s a su b n o rm a l m a g n e tic m o m en t,
1.64 B .M ., a t room te m p e r a tu r e (1 9 ). It h a s a n a n t i - a n t i c o n f ig u r a tio n ,
F ig u re 4 (1 8 ). The b rid g e d Cu a to m s a re 5.8 0 ± 0.04 % a p a r t w h ic h p r e c lu d e s
OH2
F ig u re 4 .
OH2
C u (H C O O )2 * 4 H2O S tru c tu re
in v o k in g d i r e c t o v e r la p o f C u d o r b i t a l s to e x p la i n th e s u b n o rm a l m a g n e tic
m o m e n t. M a r tin a n d W a te rm a n (22) h a v e s u g g e s t e d a s u p e r e x c h a n g e m e c h ­
a n is m th ro u g h a TT p a th w a y o f C u 3dyz a n d 3dx z o r b i t a l s a n d 2p7T o r b i t a l s o f
t h e b rid g in g fo rm ate group a s a p o s s i b l e e x p l a n a tio n for th e s u b n o rm a l m a g ­
n e tic m o m e n t.
S e v e r a l a d d i t i o n a l Cu(II) c a r b o x y l a t e s a n d p y r i d i n e - N - o x i d e co m ­
p o u n d s h a v e b e e n p r e p a r e d (Table I ) . Some h a v e p r o p e r tie s s im ila r to b i n u c l e a r C u (C H 3C O O )2 • I H 2O a n d C u C l2 • I C 5H 5NO, b u t t h e i r s tr u c tu r e s h a v e
b e e n u n e q u iv o c a lly d e te r m in e d in o n ly a few c a s e s (I, 16, 2 3 ).
- 8 T h ere a re Cu(II) c a r b o x y l a t e s (Table II) w ith n o rm a l m a g n e tic m o m en ts.
O th e r e x a m p le s o f Cu(II) c o m p o u n d s w ith n o rm al m a g n e tic m o m e n ts a r e i n ­
c lu d e d .
T a b le II
Cu(II) C o m p o u n d s w ith N orm al M a g n e tic M o m e n ts
L ig an d
Formula
(B.M. )
M a g n e tic M o m e n t3
D ic h lo ro a ce tic a c id
C u (CI2 C H C O O ) 2 • 4 H 2O
1.74
B en z o ic a c i d
.C u(C G H sC pO )2
1.72
o - H y d r o x y b e n z o ic a c i d
C u (H O C 6H 4C O O )2 • 4 H 2O
1.92
M a lo n ic a c i d
C u (C O 2 C H 2 CQO) • H2O
1.92
C u C l2
1.75
C u C l2 • 2 H 2O
1.87
Form ic a c i d
C u (H C O O )2
1.75
Form ic a c i d
C u (H C O O ) 2 * 2 H 2O
1.90
1 , 2 , 4 T r ia z o le
a Room te m p e r a tu r e
cucW
c r n " ^ chV '
X
I
H ‘
-
.
..
'
1.81
S tr u c tu r a l i n v e s t i g a t i o n of Cu(II) c o m p o u n d s w ith n o rm al and. s u b n o r­
m a l m a g n e tic m o m ents, p a r t i c u l a r l y th e c a r b o x y la te s , s e e m to in d ic a te t h a t
fo rm a tio n o f d im e ric c o m p o u n d s a n d i n c r e a s e d e l e c t r o n i n t e r a c t i o n i s de-r
p e n d e n t u p o n th e c o o r d in a tin g s t r e n g t h s o f t h e lig a n d a n d s o l v e n t . The c o ­
o r d in a tin g s tr e n g th o f t h e l i g a n d , in t u r n , i s d e p e n d e n t u p o n th e e l e c t r o n
w ith d ra w in g o r r e l e a s i n g a b i l i t y of i t s s u b s t i t u e n t s . The e x a c t p a th w a y fpr
e l e c t r o n i n t e r a c t i o n r e m a in s u n s o l v e d . I n v e s t i g a t i o n of l i g a n d s s im ila r to
- 9 c a r b o x y la te g ro u p o r p y r i d i n e - N - o x i d e h a s b e e n u n d e r ta k e n to o b ta in fu rth e r
in fo rm a tio n a b o u t th e p a th w ay .
T h e re a r e l ig a n d s s im ila r to th e c a r b o x y la te group w h o s e g e o m e trie s
m ig h t p erm it b i d e n t a t e c o o r d in a tio n a n d fo rm atio n o f b i n u c l e a r Cu(II) c o m ­
p o u n d s . The a c e ta m id e group i s a n e x a m p l e , F ig u re 5. O th e r p o s s i b l e l i ­
g a n d s a r e sh o w n in F ig u re 6 . Cu(II) c o m p o u n d s w ith l ig a n d s in F ig u re s 5
a n d 6 m ig h t p o s s i b l y i n c r e a s e th e u n d e r s ta n d in g of th e e l e c t r o n in te r a c t io n
t h a t o c c u r s in th e p r e v io u s ly m e n tio n e d b i n u c l e a r b i d e n t a t e Cu(II) com ­
pounds .
O
C a r b o x y la te G roup
F ig u re 5 .
A cetam id o G roup
C a r b o x y la t e a n d A c eta m id o G roup S im ila rity
©
O -
CH3
\
I
H2N
H2 N
NH
NH
B en z a m id in e
A c e ta m id in e
(X -am inopyridine
H
OC-p y rid o n e
1 , 8 n a p h th y rid in e
F ig u re 6 . P o s s i b l e B id e n ta te L ig a n d s
- 10 • S y n t h e s i s a n d i n v e s t i g a t i o n o f Cu(II) c o m p o u n d s w ith th e a c e ta m id o '
group (Figure 5) w a s u n d e r ta k e n a s p a rt o f g la r g e r p ro g r a m „ L ittle s u c c e s s
w a s a c h i e v e d w ith th e a c e ta m id o group d u rin g two y e a r s of i n v e s t i g a t i o n .
The r e s u l t s a r e d e s c r i b e d in A p p en d ix A.
(X -p y rid o n e (Figure 6) i s s im ila r to th e c a r b o x y la te g ro u p ; it o ffe rs
th e p o s s i b i l i t y o f b i d e n t a t e c o o r d i n a t i o n . It i s a l s o s im ila r to p y r i d i n e - N o x id e , w h ic h h a s form ed b i n u c l e a r Cu(II) c o m p o u n d s w ith u n u s u a l m ag n etic'
m o m e n ts . The p u r p o s e o f t h i s t h e s i s i s to re p o rt th e s y n t h e s i s a n d p re ­
lim in a ry i n v e s t i g a t i o n o f t r a n s i t i o n m e ta l co m p o u n d s, p a r t i c u l a r l y Cu(II) a n d
Co(II), w ith C t- p y r id o n e .
ANALYTICAL TECHNIQUES
T h is s e c t i o n d e s c r i b e s th e a n a l y t i c a l t e c h n i q u e s u s e d in t h i s stu d y .
The r e s u l t s a p p e a r in th e e x p e r im e n ta l s e c t i o n s to follow .
Cu(II) c o n c e n t r a t i o n s w e re d e te r m in e d b y io d o m e tric t i t r a t i o n a s d e ­
s c r i b e d b y K olthoff a n d S a n d e ll (24). C o (II), Ni(II) a n d Mn(II) c o n c e n t r a t i o n s
w e re fo u n d b y EDTA t i t r a t i o n s a s o u tlin e d b y W e lc h e r (25). C h lo rid e c o n ­
c e n t r a t i o n s w e re d e te r m in e d by AgNOg t i t r a t i o n w ith d i c h l o r o f l p p r e s c e i n a s
i n d i c a t o r (24). N itro g e n c o n t e n t w a s fo u n d b y th e m acro K je ld a h l m e t h o d .
T r ip lic a te s a m p l e s w e re a n a l y z e d in a l l c a s e s .
In fra re d s p e c t r a w e re ru n o n a B eckm an I R - 4 s p e c tr o p h o to m e te r b e ­
t w e e n 5 ,0 0 0 - 6 5 0 cm - -*-. The s a m p le s w e re p re p a re d a s m ic ro KBr p e l l e t s . In
a l l c a s e s a i r w a s th e r e f e r e n c e m a t e r i a l .
U l t r a v i o l e t a n d v i s i b l e s p e c tr a o f s o l u t i o n s w e re t a k e n a t room te m ­
p e r a tu r e w ith a B eckm an D K -2 s p e c tr o p h o to m e te r e q u ip p e d w ith I cm c e l l s
a n d s ta n d a r d lig h t s o u r c e s . In a l l c a s e s , pure s o lv e n t w a s th e r e f e r e n c e
■
m a t e r i a l . C o n c e n t r a t i o n s of IO- ^ M a n d IO- ^ M w e re u s e d for v i s i b l e a n d
u l t r a v i o l e t r e g io n s , r e s p e c t i v e l y .
D if f u s e r e f l e c t a n c e s p e c tr a o f s o l i d s w e re c o l l e p t e d w ith a Beckm an
M o d e l B s p e c tr o p h o to m e te r e q u ip p e d w ith a d iff u s e r e f l e c t a n c e a tta c h m e n t
# 1 2 4 0 0 a n d a 2 ,0 0 0 m egohm p h o to tu b e r e s i s t o r . The s tu d y w a s lim ite d to t h e
ra n g e 7 0 0 -3 5 0 mju by th e i n s tr u m e n t. M a g n e s iu m c a r b o n a te w a s u s e d a s t h e
stan d a rd .
- 12 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 p o w d e r s a m p l e s w e re d e te r m in e d by
th e G ouy m e th o d u t i l i z i n g a M e ttJ e r a n a l y t i c a l b a la n c e , H a r v e y - W e lls M o d e l
L - 44V e le c tr o m a g n e t a n d a M a g n io n m o d e l #H S425 p o w e r s u p p ly . The m a g ­
n e t w a s e q u ip p e d w ith 4 in c h t a p e r e d p o le c a p s a n d a v a r i a b l e g a p . The.
s a m p l e s w e re s u s p e n d e d in a s p e c i a l l y d e s i g n e d D e w a r f l a s k p la c e d b e ­
t w e e n th e p o le c a p s . The s u s c e p t i b i l i t i e s r e p o r te d , e x c e p t t h o s e of
d ic h lo ro -m o n o -(O L -p y rid o n e ) co p p er(II), w e re d e te r m in e d a t 80 °K ., 210°K.,.
2 5 0 ° K . a n d 2 9 8 ° K . L iq u id a ir w a s u s e d to r e a c h 8 0 °K . The in te rm e d ia te
te m p e r a t u r e s w e re o b t a i n e d b y p la c i n g s l u s h e s o f dry i c e a n d C H Clg (?10o K)
a n d C C I 4 (250°K) in th e D e w a r f l a s k . Four ^ield s tr e n g th s w e re u s e d in th e
s tu d y . T r ip lic a te m e a s u r e m e n ts w e re m a d e a t e a c h te m p e r a tu r e a n d f ie ld
s t r e n g t h . The a v e r a g e of th e m e a s u r e m e n ts a t e a c h te m p e r a t u r e a n d f i e l d
s tr e n g th w a s u s e d to c a l c u l a t e gram s u s c e p t i b i l i t i e s from th e e g u a tiq p :
Xg
=
g' =
g' =
Aw =
d
=
■A =
H =
qg lAw
dAH2
gram s u s c e p t i b i l i t y '
L an d e g fa c to r
s ta n d a r d g r a v i t a t i o n a l c o n s t a n t
w e ig h t (field a p p l i e d ) - w e i g h t (no fie ld )
s a m p le d e n s i t y
c r o s s e c t i o n a l a r e a o f Q puy tu b e
m a g n e tic f ie ld s tr e n g th
■
- 13M a g n e tic m o m en ts w e re c a l c u l a t e d from th e e q u a tio n :
.Meff
SXmkT
£2 N
e ff = 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 s
•
X m = X g tim e s s a m p le m o le c u la r w e ig h t
k = B o ltz m a n n 's c o n s t a n t
T = d e g r e e s K elv in
• /3 = 0.917 x l O " 20
N - A v o g a d ro 1s num ber
To f a c i l i t a t e c a l c u l a t i o n o f th e m a g n e tic s u s c e p t i b i l i t i e s a n d m om ents, ..a
F o rtra n c o m p u te r program w a s u s e d . The c o m p u te r u s e d w a s th e m o d ified
IBM 1620 a v a i l a b l e a t th e M o n ta n a S ta te U n iv e r s ity C o m p u tin g C en ter.
C o r r e c tio n s for d ia m a g n e tic a to m s w e re a p p l i e d in th e c a l c u l a t i o n s . M a g ­
n e tic f ie ld s tr e n g th s w e re d e te r m in e d u s in g H g C o (C N S )i^ a s th e s ta n d a r d
(26).
X - r a y p o w d e r d if f r a c tio n d a ta w a s c o l l e c t e d w ith a G e n e r a l E le c tric
d if f r a c to m e te r u n it b y n o rm al c r y s t a l l o g r a p h i c p r o c e d u r e s . X -ra y s in g le
c r y s t a l d a ta w a s c o l l e c t e d by b o th W e i s s e n b e r g a n d P r e c e s s i o n m e th o d s .
C r y s t a l p a r a m e te r s w e re c a l c u l a t e d u s in g s ta n d a r d fo rm u lae from B uerger
(27).
M o l e c u l a r w e ig h ts w e re d e te r m in e d e b u l l i o s c o p i c a l l y b y th e C o ttr e ll
t e c h n i q u e (98). A B eckm an d if f e r e n t i a l th e rm o m e te r w a s e m p lo y e d in th e d e ­
t e r m i n a t i o n s . The o s m o m e tric d e te r m in a tio n s re p o rte d w e re perform ed b y Dr.
W. W. P a u d le r o f th e D e p a rtm e n t o f C h e m istry , O hio U n iv e rs ity , A t h e n s ,
. O h io .
EXPERIMENTAL PROCEDURES AND RESULTS
P u r if ic a t io n o f g - p y r i d o n e
CX-pyridone (C 5H 5 NO) p u r c h a s e d from A ceto C h e m ic a l C o m p an y w a s
p u rif ie d by r e c r y s t a l l i z a t i o n from b e n z e n e . The c r y s t a l s w e re w h ite a n d
m e lte d a t 1 0 6 .5 - 107°C . (X -pyridone w a s a l s o id e n tif ie d s p e c to p h o tm e tr iq a l l y a n d by n itr o g e n a n a l y s i s (14.5% fo u n d , 14.7% c a l c u l a t e d .
F ig u re 7 is a n in fr a r e d s p e c tru m o f <X -pyridone. F ig u r e s 8 to 11 r e p ­
r e s e n t th e u l t r a v i o l e t s p e c t r a of <X-pyridone in HgO, C g H g O H , C H 3C N a n d
H C O N tC H g ^ ; T a b le III l i s t s th e u l t r a v i o l e t a b s o r p tio n b a n d s a n d th e ir
m o la r a b s o r p t i v i t i e s .
3U0
1200
WAVENUMBER IN KAYSERS
F ig u re 7 .
In fra re d S p e c tru m of c t- p y r id o n e
- 15-
F ig u re 8 .
F ig u re 9 .
U ltr a v io le t S p ectru m of <X-pyridone in H 2O
U l tr a v io le t Spectru m o f oc-pyridone in CgH ^O H
— 16 —
F ig u re 10.
F ig u re 11.
U l tr a v io le t S p ectru m o f <X-pyridone in C H gCN
U l tr a v io le t Spectru m o f OC-pyridone in H C O N (C H g)2
-17T a b le III
U l tr a v io le t S p e c tr a l Bandp for CL-pyridone
S o lv e n t
C o n c e n tr a tio n
H 2O
1.73 x IQ" 4 M
• C 2 H 5OH
1.78 x 10-4 M
• C H gC N
2 ,0 2 .^ IO" 4 M
Xmax (m^i)
,
H C O N (C H g )2
'
1.81 x 10-4 M
223.
' 293
226
298
227
229
2 3 5 (s h )a ,
302
312(sji)
237(sh)
305
315(sh)
335(sh)
: (M olar
a b s o r p tiv ity )
£ m ax
7.17
5.72
8.32
5.23
7.57
. 7.53
x
x
x
*
x
x
IO3
IO3
IO3
IO3
IO3 •
IO3
. 4.85 x IO3
“ “ ——T — ~
--- T —
4.80 x IO3
4.42 x IO3
--- ---------
a S h o u ld e r
P r e p a r a tio n o f A nh y d ro u s M e t a l (II) C h lo r id e s
A nhydrous m e ta l c h lo r id e s u s e d th ro u g h o u t th e s tu d y .w e r e p re p a re d a s
o u tlin e d b y P ray (28) from c o m m e rc ia lly a v a i l a b l e h y d r a t e s . They w e re '
s to r e d o v e r a n h y d ro u s CaSOz|. in t i g h t l y c a p p e d c o n t a i n e r s . .
S o lv e n t P u rity
S o lv e n ts in c o r p o r a te d in th e s tu d y w e re e ith e r MGB s p e c f r o - q u a Iity
'
r e a g e n t s o r t h e highest; p u rity r e a g e p t a v a i l a b l e . .W h en w a t e r c o n te n t w a s ir>
d o u b t in a l c o h o l s , p a r t i c u l a r l y CHgOH a n d C g H ^ O lf , t h e y w e re re flu x e d ■
o v e r Mg tu r n i n g s for tw e lv e h o u rs a n d t h e n d i s t i l l e d . The f r e s h ly d i s t i l l e d
a l c o h o l s w e re u s e d a s q u ic k ly a s p o s s i b l e to m in im ize u p ta k e o f a tm o s ­
p h e ric w a t e r .
.
- 18 -
S y n t h e s i s o f D ic h lo rp T m o n o -tX -'p y n d o n e M e ta l (II) C o m p le x e s
To p re p a re C u C lg • I C gH^NO, 1:1 m o la r r a t i o s of a n h y d ro u s C p C l2
a n d p u r if ie d cXrPyridone w e re u s e d . The r e a c t a n t s w e re d i s s o l v e d in m in i­
mum a m o u n ts of C gH gO H a n d th e o f-p y fid d n e s o lu tio n w a s q d d e d d ro p w is e
fo t h e Cu(II) s o lu tio n w ith s ti r r i n g . P r e c i p i t a t i o n o c c u r r e d a f t e r a p p ro x i­
m a te ly o n e - h a l f o f th e cd-pyridone s o lu tio n h a d b e e p a d d e d . Thp s o lid p ro ­
d u c e d w a s a n o ra n g e po w d er; th e f i l t r a t e w a s g r e e n . C o o lin g th e f il tr a te
p ro d u c e d m ore o f th e o ra n g e s o l i d . R e c r y s t a l l i z a t i o n from C gH gC H p ro d u c e d
n e e d l e - l i k e c r y s t a l s . ■A n a ly s is o f th e c o m p o u n d i n d i c a t e d th p e m p e r ic a l
m o le c u la r form ula w a s C uC lg • I CgH gNO .
The e a s e w ith w h ic h th e c o m p o u n d w a s p ro d u c e d p ro m p ted a l i t e r a t u r e
s e a r c h to d e te r m in e if c o m p o u n d s s im ila r to (X-pyrjLdone h a d b e e n u s e d a s
l ig a n d s w ith t r a n s i t i o n m e tp l i o n s . A S e rie s of co m pounds', MXg •, Ln. (M =
m e ta l i o n , X = h a lid e , n itr a te , p e rc h lo r a te , L = Pyridine=-N-Oxide (C gH sN O ),.
n = I, 2, 3, 4) h a d b e e n p re p a re d by Q u a g lia n o (29). The c o m p o u n d s h a d b e e n
s y n t h e s i z e d a n d r e c r y s t a l l i z e d from e t h a n o l i c s o l u t i o n s . A few of t h e s e ' . .
c o m p o u n d s e x h ib ite d s u b n o rm a l m a g n e tic m o m e n t s . G n e o f th e c o m p o u n d s
w ith a low m o m e n t, C u C lg • I C gHgNG, h a d b e e n sh o w n to b e a n o x y g e n
b rid g e d b i n u c l e a r co m p o u n d (Figure I , p a g e 3). This co m p o u n d hgd a m a g ­
n e tic m om ent of 0.85 B.M . B ecause! som e of th e p y r i d i n e - N - o x i d e com ­
p o u n d s e x h ib ite d s u b n o rm a l m a g n e tic m o m e n ts a n d CP-pyridone w a s s t r u c . t u r a l l y s im ila r to p y r id i n e - N - o x id e , s y n t h e s i s of a r e l a t e d s e r i e s , MXg • Lj ■
(M = t r a n s i t i o n m e t a l , X = c h lo rid e ; L = c t-p y rid o n e ), w a s u n d e r ta k e n .
The r e a c t a n t s w e re m ix e d a s p r e v io u s ly d e s c r i b e d for th e s y n t h e s i s of
- 19
d ic h lo ro -m o n o -O L -p y rid d n e - c o p p e r ( I I ) .
C o m p o u n d s w ith th e e m p iric a l
form ula M Clg ° I C 5H 5NO h a v e b e e n s y n t h e s i z e d u s in g Cu(II), Co(II), Ni(II)
a n d Mn(II) c h lo r id e s a n d r e c r y s t a l l i z e d from C g H g O H ., T a b le IV l i s t s th e r e ­
s u l t s o f e le m e n ta l a n a l y s e s perfo rm ed a s d e s c r i b e d in th e a n a l y t i c a l s e c ­
ti o n .
T a b le IV
M Clg • I CgH gNO E le m e n ta l A n a ly s e s
Cu(II)
Co(II)
Ni(II)
Mn(II)
.% c r
%M
M etal
Found
C alc .
2 7. 7+0.23
2 7.7
2 6. 0+;Q. 40
26.2
2 5 .8 + 0 .1 7
26.1
■ 2 4 .3 + 0 .7 5
24.9
30 .9 + 0 .2 3
30.9
3 1 .5 + 0 .1 7
31.6
31. 0+ 0.00
31.6
3 1 .0 + 0 .1 7
32.1
.
%N
C o lo r
5 .8 + 0 .1 7
■o ra n g e
6.1 .
6 .4 + 0 4 1
b lu e v io let
6.2
6 .4+ 0.33 ' s a lm o n
6.2
6 .5+ 0,28 . o f f - w h ite
. 6.3
N a tu re
n e e d le -lik e
cry stals
n p e d le-lik e
c ry sta ls
pow der
p o w d er
M a g n e tic s u s c e p t i b i l i t i e s a n d m o m en ts, c a l c u l a t e d a s d e s c r i b e d in
t h e a n a l y t i c a l s e c t i o n , a re l i s t e d in T a b le V.
T a b le VI i n d i c a t e s d s p a c i n g s a n d 6 a n g l e s o f th e s ix m o s t in t e n s e
p o w d e r d if f r a c tio n lin p s , o b ta in e d w ith th e G e n e r a l E l e c tr ic d iffra c to m e te r,
for e a c h o f th e c o m p l e x e s . The d v a l u e s w e re c a l c u l a t e d from th e e q u a tio n ;
w h e re
nX
n
A
d
0
=
=;
=
=
=
2 d s in 0
I
w a v e le n g th o f in c id e n t r a d i a t i o n
d i s t a n c e b e t w e e n la y e r s
d if f r a c tio n a n g le
—20 —
T a b le V
M C lg • I C 5H 5NO M agnetic, S u s c e p t i b i l i t i e s a n d M o m e n ts
M eta l '
T em p . °K
X m ( ° 9 s-/ e s u ) x IO6
M a g n e tic S u s c e p t i b i l i t y
(B.M.)
M a g n e tic Mom
80°
298°
80°
21 0 °
2 50°
298°
80°
2100.
2 50°
298°
800
210 °
2 50°
298°
6,970
1,540
53,300
21,100
17,000
11,900
31,800
8,600
7,000
5,400
52,400
19,800
17,700
14,600
. 2.13
1.93
5.91
6.03
5.90
5.39
4.57
3.86
3.80
3.65
5.86
5.83
6.03
5.97
Cu(II)
Co(II)
•
Ni(II)
Mn(II)
■,
.
T a b le VI
MQ12 • I C 5H 5NO P o w d er D iff ra c tio n D a ta
Co(II)
Cu(II)
Ni(II)
d
0
■d
R e l.
In t.
e
d
3.9
11.3
100
3.9
1%3
100
3JB
11.6
5.0
8.8
70
4.8
9.2
. 85
4.7
7.5
5.9
75
5.9
7.5
70
9.1
4.9
•25
7.3
6.1
10.9
4.1
25
8.9
14.4
3.1
50
14.8
*Very i n t e n s e
0
Mn(II)
R e l.
In t.
R el.
In t.
d
R el.
• Int.-
100*
9
3.9
11.3
100*
9.4
75
4.8
9.2
80
5.8
7.6
65
5.8
7.6,
60
90
7.2
6.2
70
.7.2
6.2
90
5.0
70
8.9
5.0
40
8.9
. 5.0
90
3.0
60
14.9
3.0
70 '
14.6
3.1
75
- 21 S in g le c r y s t a l x - r a y d if f r a c tio n d a ta sh o w th e Cu(II) c o m p le x i s t r i ­
c l i n i c w ith s p a c e g ro u p 'PT. I ts c e l l d im e n s io n s a re : a = 9 . 9 3 b = 9 .9 4 2 ,
c = 3.95 2 w ith CL = 90.9°, (5 = 92.9° a n d Y - 113.2°. T here a r e two form ula
u n its p e r u n it c e l l . The c o b a l t c o m p le x i s m o n o c lin ic a n d o f s p a c e g ro u p
CZyc ’
I ts c e l l d im e n s io n s a re ; a = 24.8 2 , b = 16.7.2, c = 8.7 2 w ith
Y = 94°. T h ere a re 16 form ula u n its p e r u n it c e l l .
The u l t r a v i o l e t s p e g tr a o f th e M Clg • I C 5U 5NO c o m p le x e s a re e s s e n ­
t i a l l y i d e n t i c a l to t h o s e o f d t-p y rid o n e p r e v io u s ly sh o w n in F ig u re s 8 to 11,
p a g e s 15 a n d 16. The c o m p le x e s , in g e n e r a l , e x h ib it lo w e r m o lar a b s o r p t i v i t i e s th a n fre e o d - p y r id o n e . T a b le VII l i s t s th e u l t r a - v i o l e t a b s o r p tio n
b a n d s a n d m o la r a b s o r p t i v i t i e s of th e c o m p l e x e s .
T a b le VII
M Clg • I C 5H 5NO U l tr a v io le t A b so rp tio n Bands a n d M o la r A b s o r p tiv itie s
Cu(II)
(mju)
A m ax
S o lv e n t
H 2O-
C 2H 5OH
223
292
. 226
298
C H 3CN
H C O N (C H 3) 9
2 2 3 (sh )
226
2 3 4 (sh )
257
305
310(sh)
328(sh)
£ m ax
6900
6130
742 0
6220
9330
2670
5290
Cp(II)
(mpt)
A m ax
222
294
Ni(II)
(nyj)
6 max A m ax 6 m ax
7700 223
6420 291
227
298
8480
5280
226
2 2 9 (sh )
233(sh)
257 ■
302
312 (sh)
328(sh)
9430
227
298
8080
6480
8530
. 5580
Mn(II)
(nyj)
A max
223
2 30(sh)
. 294(sh)
315(sh)
226
298
6 m ax
8450
6750
8530
5760
2870
5330
5280
305 .
315(sh)
330(sh)
305
315(sh)
332 (sh)
11600
- 22 V is ib le s p e c t r a for t h e s e c o m p le x e s a r e sh o w n in F ig u r e s 1 2 - 2 0 .
T h e ir a b s o r p tio n b a n d s a n d 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 T ab le VIII.
F ig u re 12.
V is ib le S p ectru m o f C u C lg • I C 5H 5NO in H 2O
Fig u re 1 3 . V is ib le Spectrum o f C uC lg • IC 5 H 5 N O in CgHgOH
- 23 -
___I____________________ I____________________ i----------------------------1—
400
F ig u re 14.
F ig u re 15.
500
mu
600
700
V is ib le S pectru m o f C u C lg • I C 5H 5N O in C H gCN
V is ib le A b so rp tio n S p e c tru m o f C oC lg • I C 5 H 5 NO in HgO
- 24 I
F ig u re 16.
F ig u re 17.
V is ib le A b so rp tio n S p ectru m of C oC lg * I CqjH 5NO in C gH ^O H
V is ib le A b so rp tio n S p ectru m of C 0 C I 2 • I C ^ H ^ N O in H C g C N
-25-
F ig u re 18.
F ig u re 19.
V is ib le A b so rp tio n S p ectru m o f N iC ^ • I C ^ H 5NO in HgO
V is ib le A b so rp tio n Spectru m of NiClg • I C 5 H 5 NO in C gH gOH
—26 —
F ig u re 2 0 .
V is ib le A b so rp tio n S p ectru m o f N iC lg • I C gH gN O in H C O N C C H g^
T a b le VIII
. M CIg • IC 5 H 5 N O V is ib le B an d -S p ectra a n d M o la r A b s o rp tiv itie s
• C u(H )
X m ax
• € .m ax
(mu)
S o lv e n t
H2O
C oH cO H
z. O
.
790
128
49:8
880
164.
5 75(sh)
612 (sh)
638
6 55(sh)
6 65(sh)
4 50.
C H 3C N
H C O N ( C H 3) 2 - .
'
. C o(II)
X m ax
E m ax
(mu)
. 931
:
556
5 70(sh)
' ■590
6 1 0(sh)
650 (sh)
660
5.1
N i(II)
X m ax
(mu)
385
7 0 0 (v .b .)
E m ax
6.2
2.5
413
10.7
410
575(sh)
602
51.00
46.0
28.0
168.0
2 58.0
.
2 66.0
402.0
—28 —
D iffu s e r e f le c ta n c e s p e c tr a for th e c o m p le x e s a re s h o w n in F ig u re s
2 1 -2 4 .
F ig u re 2 1 .
D iffu s e R e fle c ta n c e S p ectru m o f C uC lg • I C5H5NO
F ig u re 2 2 .
D iff u s e R e f le c ta n c e Spectrum of C o C lg • I C 5 H 5 NO
-29-
F ig u re 2 3 .
D iffu s e R e fle c ta n c e S p ectru m of N iC lg • I C g H 5NO
F ig u re 2 4 .
D iff u s e R e f le c ta n c e Spectru m of M nClg • I C 5 H 5NO
- 30 In fra re d s p e c tra o f th e c o m p le x e s a ls o re s e m b le th e sp e c tru m o f Oip y r id o n e . Some c h a r a c t e r i s t i c a b s o r p tio n b a n d s u s e d fo r in te r p r e ta tio n e x ­
h ib it s h if ts in fre q u e n c y a n d in te n s ity . The in fra re d s p e c tra o f th e com ­
p le x e s a re sh o w n in F ig u re s 2 5 - 2 8 . Band a s s ig n m e n ts a n d in te r p r e ta tio n o f
th e o b s e r v e d s h if ts a p p e a r in th e d is c u s s io n s e c tio n o f th e t h e s i s .
M o le c u la r w e ig h t d e te rm in a tio n s w ere perfo rm ed a s p re v io u s ly d e ­
s c r ib e d for a l l b u t th e M n(II) c o m p le x . The r e s u lts a re l i s t e d in T ab le IX.
P e rc e n t T
T
"I
- r - f ......1
c m 'l
F ig u re 2 5 .
In fra re d S p ectru m o f C uC l2 • I CcjH 5NO
P e rc e n t T
— 31 —
20%
In fra re d S p ectru m o f C oC lg • I C 5H 5NO
P e rc e n t T
F ig u re 2 6 .
2000
F ig u re 27.
In fra re d S p e c tru m o f NiClg • I C 5 H 5 NO
- 32 -
I -----1
... j
U______ U
F ig u re 2 8 .
In fra re d S p ectru m o f M nC lg • I C5H 5N O
T a b le DC
M C lg • I C5H 5N O M o le c u la r W e ig h t by D e te rm in a tio n s
Found
E m p iric a l
M o le .W t.3
C om pound
S o lv e n t
M eth o d
C u C l2 . I C 5H 5NO
C H 3CN
C 2H 5OH
H C O N (C H 3)2
H C O N (C H 3) 2
E b u llio s c o p ic
O sm o m etric b
E b u llio s c o p ic
E b u llio s c o p ic
865
975
84
135
230
230
230
135
C 0C I2 • I C 5H 5
C 2 H 5OH
C 2 H 5OH
C 2 H 5OH
H C O N (C H 3)2
E b u llio s c o p ic
O sm o m etric
O sm o m etric
E b u llio s c o p ic
118
1,195
1,079
115
225
225
225
225
N iC l2 • I C 5H 5
H C O N (C H 3)2
E b u llio s c o p ic
40
225
C uC l2
a T h e o re tic a l m onom er m o le c u la r w e ig h t
b D e te rm in e d by Dr. W. W. P a u d le r7 D e p a rtm e n t o f C h e m is tr y , O hio U n iv e r­
s ity
-
33
-
S y n th e s is o f D ic h lo ro -n - & -p y rid o n e M e ta l (II) .C o m p le x e s.
Q u a g lia n o h a d a ls o p re p a re d C uC lg • 2 C5H 5N O (p y rid in e - N -o x id e ), a
c h a r tr e u s e pow der, a n d b lu e C oC lg • 3 C 5H 5N O (p y rid in e -N -o x id e ), S y n th e ­
s e s in w h ic h a rb itra ry C u (II): dC -pyridope m o lar r a tio s w e re u s e d , p rio r to
s y n th e s is o f m o n o -c t-p y rid o n e c o m p le x e s , h a d p ro d u c e d a c h a r tr e u s e p o w d e r
w h o se e le m e n ta l a n a ly s e s (19.5% C u , 21.7% C l, 9.3% N) w e re c lo s e to th e
c a lc u la te d v a lu e s o f C uC lg , 2 C 5H 5N O (c t-p y rid o n e). T h e re fo re , I c o p p e r(ll):
2 oL -pyridone m o lar r a tio s (e th a n o lle s o lu tio n s ) w ere m ix e d a s b e fo re (d ro p w is e , p a g e 18) a n d a c h a r tr e u s e p o w d er p r e c ip ita te d , a f te r a p p ro x im a te ly
o n e - h a lf o f th e C u(II) h a d b e e n a d d e d . O n e c o b a lt (II): 3 o ^ p y rid o n e e th a n o l­
le s o lu tio n s w e re r e a c te d in th e sam e m a n n er an d a b lu e c r y s ta llin e s o lid .
p r e c ip ita te d . A ll o f th e p r e v io u s ly d e s c r ib e d m e th o d s o f id e n tif ic a tio n w e re
p e rfo rm ed o n th e s e c o m p le x e s e x c e p t m o le c u la r w e ig h t d e te r m in a tio n s . The
r e s u l t s o f t h e s e m e th o d s for b o th c o m p le x e s h a v e b e e n c o m b in e d ,for p r e s e n ­
t a t i o n . E le m e n ta l a n a l y s e s a p p e a r in T a b le X,
T a b le X
C uC lg • 2 C 5H 5NO a n d C oC lg
3 C5H 5N O E le m e n ta l A n a ly se s
%M
%c r
% N
C o lo r
Cu. Found
. C a lc „
2 0.0+0.17
19.6
22.2+0.2 8
21,9
8,65+0.16
8.63
. c h a r tr e u s e
C o Found
C a l.
14.6±0.00
14.2
17.65+0.06
17.1.
9.8+0.33
10.1
X -ra y p o w d er d a ta for th e s ix
a p p e a r in T a b le X I.
b lu e
N a tu re
pow der
c r y s ta llin e
s t in te n s e p o w d er d iff ra c tio n lin e s
34 ”
'
T a b le XI
C uC lg • I C 5H5NO a n d C 0C I2 • 3 C 5H 5NO P ow der D iffra c tio n D ata
C u(II)
9 •
4.2
5,0
5,8
7.1
9.6
10.0
C o(II)
. 3
R e l.
In t.
9
d
R e l.
In t.
10.5
8.84
7.62
6,23
4.6?
4.44 •
90
95
100
95
80
85
6.1
8.2
8.3 •
9.2
13.4
15,2
7.25
5.40
5.34
4.q2
3.33
2.34
90
70
70
1Q0
60
55
A gain th e u ltr a v io le t s p e c tr a re s e m b le th o s e o f o t-p y r id p n e . The a b ­
s o rp tio n b a n d s a n d m o le c u la r a b s o r p tiv itie s a re lis t e d in T a b le X II.
T a b le XII
C uC lg • 2 a - p y r id o n e g n d C pC lg • 3 <%-pyridpne U.V. S p e p tra l Bands
C o n c e n tra tio n
(m olar
a b s o r p tiv ity )
E m ax
(mu)
Amax
C e m p le x
S o lv e n t
C uC l2 • 2 OL
H2G
2 .I l x l O - 5 M
223
293
1.32 X lO4 . .
1.33x104
C H 3CN
1.06 x IO- 5 M
2 2 5 (sh )9
2 3 0 (sh )
3 3 4 (sh )
303
3 1 5 (sh ).
3 3 0 (sh )
1.1'3 x IO4
C o C lg - 3OL
H2O
C2 H 5OH
CHgCN
a S h o u ld e r
'
■
4.08 x IO- 6 M
223
295
4.28 x IO- 6 M
. 225
305
4.53 x IO- 6 M
'
2 30 (sh )
2 3 5 (sh )
303
31 5 (sh )
33 0 (sh )
'
2.71x104
2 .2 1 x 1 0 4
2.33x10.4
1.48x10 4
1,76x104
.
.
- 35 F ig u re 2 9 -3 3 a re th e v is ib le s p e c tr a o f th e c o m p le x e s a n d T a b le XIII
l i s t s th e a b s o r p tio n b a n d s a n d th e ir m o la r a b s o r p t i v i t i e s .
F ig u re 2 9 .
F ig u re 3 0 .
V is ib le A b so rp tio n S p e c tru m o f C uC l2 • 2 C 5H 5N O in H2O
V is ib le A b so rp tio n S p ectru m o f C u C l 2 • 2 C 5 H 5 NO in C H g C N
- 36 -
F ig u re 3 1 .
V is ib le A b so rp tio n S p ectru m o f C oC lg • 3 C gH gN O in HgO
F ig u re 32 . V is ib le A b so rp tio n S p ectru m of C oC lg • 3 C 5 H 5 NO in C gH gOH
- 37-
F ig u re 3 3 .
V is ib le A b so rp tio n S p ectru m o f C oC lg • 3 C 5H 5N O in C H 3C N
T a b le XIII
C uC lg • 2 C 5H 5N O an d C oC lg • 3 C 5H 5N O V isib le A b so rp tio n Bands
C o m p lex
S o lv e n t
C uC l2 ■ 2 C5H 5N O
H2O
5.28 x IO- 3 M
786(v. b .) a
C H 3CN
1 .0 6 x 1 0 -3 m
875(v. b . )
450
H 2O
C 2 H 5OH
4.08 x IO- 3 M
4.28 x IO- 3 M
490
5 7 5 (sh )
6 0 0 (sh )
640
C oC lg • 3 C 5H 5NO
C H 3CN
a Very b ro a d
C one.
(mu)
X m ax
4.53 x IO- 3 M
565
5 75(sh)
60 0 (sh )
61 3 (sh )
660
(m olar
a b s o rp tiv ity )
G m ax
13
75
775
7
152
97
159
— 38 —
F ig u re s 34 an d 35 a re th e d iffu s e r e f le c ta n c e s p e c tr a o f th e com ­
p le te s .
F ig u re 3 4 .
D iffu s e R e fle c ta n c e S p ectru m of C u C lg • 2 C5H5NO
Fig u re 3 5 .
D if f u s e R e f le c ta n c e S p ectru m of C o C lg • SC ^H ^N O
- 39 The in fra re d s p e c tr a o f t h e s e c o m p le x e s a ls o re s e m b le th e C t-p y rid o n e
sp e c tru m w ith d if f e r e n c e s s im ila r to th e m o n o -Q '-p y rid o n e c o m p le x e s . The
s p e c tra a p p e a r in F ig u re s 36 an d 37. Band a s s ig n m e n ts a n d in te r p r e ta tio n o f
th e o b s e r v e d s h if ts a g a in a p p e a r in th e d is c u s s io n s e c tio n o f th e t h e s i s .
E-H —
<D-----
----------- 3 p —
F ig u re 3 6 .
In fra re d S p ectru m o f C uC lg • 2 C5H 5N O
P e rc e n t T
- 40
Iooo
F ig u re 37.
In fra re d S p ectru m o f C oC lg • 3 C5H 5N O
T he m a g n e tic s u s c e p t i b i l i t i e s a n d m o m en ts fo r th e c o m p le x e s a p p e a r
in T a b le XIV.
T a b le XIV
C u C l2 • 2 C 5H 5NO a n d C 0C I2 • S C 5H 5NO
M a g n e tic S u s c e p ti b ilitie s a n d M o m en ts
C o m p lex
Temp.
X m (cgs, e s u ) x lO 6
M a g n e tic S u s c e p tib ility
(B.M.)
M a g n e tic M om ent
C u C l2 • 2 C 5H 5NO
80°
210°
2 50°
298°
4,700
2,500
2 ;ioo
1)400
1.76
2.06
2.06
1.82
C 0C I2 * 3 C 5H 5NO
800
210°
2 50°
298°
32,200
13,800
11,400
9,600
4.59
4.87
4.82
4.85
DISCUSSION
!D ic h lo ro -m on o -# -p y rid o n e M e ta l(II) C o m p le x e s
The in fra re d s p e c tr a o f th e M C lg • IC 5 H 5 N O c o m p le x e s (F ig u res 2 5 28, p a g e s 3 0 -3 2 ) sh o w s h if ts in a b s o r p tio n e n e r g ie s a n d in te n s itie s , in im ­
p o rta n t re g io n s o f th e s p e c tru m . K a trits k y (30), M a s o n (31) a n d o th e rs (3 2 38) h a v e e x a m in e d th e in fra re d s p e c tr a o f a -p y rid o n e a n d h a v e a s s ig n e d
m o s t o f th e o b s e r v e d a b s o rp tio n ; b a n d s to th e v ib ra tio 'p s e x p e c te d to o c c u r
w ith in th e m o l e c u l e The a c c e p te d lite r a tu r e v a lv e s fo r (% -pyridone a re
. sh o w n in T a b le XV w ith th e b a n d s o b s e r v e d in t h is , s tu d y fo r Od-pyridorie arid
th e four M C lg • I C5H 5N O co m p o u n d s (F ig u re s 2 5 -2 8 , p a g e s 3 0 -3 2 ). The
sy m b o ls "v; j3 a n d
a re th o s e u s e d b y M a s o n ; 'Ir' r e p r e s e n ts th e fu n d a m e n ta l
s tr e tc h in g v ib ra tio n b e tw e e n b o n d e d a to m s .
r e p r e s e n ts th e in - p l a n e - ■.
b e n d in g v ib ra tio n a n d Y r e p r e s e n ts th e o u t- o f - p la r ie b e n d in g v ib ra tfo n . The
s h if ts o b s e r v e d in th e a b s o r p tio n e n e r g ie s a n d i n t e n s i t i e s in th e v N - H ,
ZzC = 0, /S n -H a n d $NT-H re g io n s in d ic a te t h a t CZ-Tpyndone i s p ro b a b ly c o ­
o rd in a te d to thfe m e ta l io n s th ro u g h th e o x y g e n a to m . F re e (% -pyridone h a s .
b e e n sh o w n to b e a hydroge-n b o n d e d d im e r (F igure 38) in th e c r y s ta llin e
s t a t e (30). The v N - H p e a k in c r y s ta ll in e O1^ p y rid o n e is b ro a d an(d a t lo w e r
e n e r g ie s (due to in te rm o le c u la r hydrogen, b o n d in g ) th a n n o rm a lly e x p e c te d "
fo r fre e V N -H V ib ra tio n ; a fre e V N -H p e a k n o rm a lly a p p e a r s a t 3400 cm - *.
If th e v N - H p 6 a k s h if ts to h ig h e r e n e r g ie s ,
in c r e a s e d f r e e . N - H
th is i s art. in d ic a tio n of
a n d d e c r e a s e ^ h y d ro g e n b o n d in g ;
it s u g g e s ts
th a t c o o rd in a tio n is n o t o c c u rrin g a t th e n itro g e n a to m . All fo u r O -p y rid o n e
c o m p le x e s e x h ib it IZ-NH s h if ts to h ig h e r e n e r g ie s (3100 c m " ^
^
— 42 T a b le XV
In fra re d Band A ss ig n m e n ts M CI2 • I C5H 5N O C o m p le x e s
A ssig n m e n t
zz-N-H
L it. V alu es
(X -pyridone
C u(II)
C o(II)
N i(II)
M n(II)
3250m
3150m
3225b
315 0 s
325 0 s
3 150w
345 0 s
3 2 0 0 -3 1 0 0
s tr o n g , b ro a d
3 1 0 0 s*
TzC=O
1 6 6 5 - 1650s
1685s
1655m
1645m
1600s
1685s
VRing . F r e q .
1 6 1 9 - 1570s
1560-1585m
1501- 1472w(m)
1 4 5 5 - 1415w(m)
1615m
1460w
1440m
1610s
1550w
1475w
1415s
1602s
1545m
1465w
1405s
1610s
1550m
1465m
1420s
1640s
1570m
1485w
1440s
^ -N -H
(am ido N -H )
1600m
1615m
1610s
1602s
1610s
1640s
j5 - C - H
1318- 1242m
1 1 8 2 - 1 154m
1 1 4 4 - 1138m
1 0 1 8 - IOlOw
1245s
1160s
1100s
IOlOw
1278m
1 170w
1105w
IOlOw
1285m
1170m
1 105w
10102
1280m
1170s
1 100m
1005s
1290m
1185s
1110m
1010s
YCH
8 4 2 -8 3 2 m
850w
865m
865m
865s
870s
YNH
82 0 re g io n
720 re g io n
785s
735s
775s
730s
780s
720m
775s
725s
780s
730s
* s = s tr o n g , m =m edium , w = w e a k , b = b ro ad
F ig u re 3 8 . O d-pyridone (C5H5NO) S tru c tu re
f
;
..
:
.
3 1 5 0 -3 2 5 0 cm"1^). T he /Sn -H a n d KN-H p e a k sh ifts- a ls o s u p p o rt d e c r e a s e d ,
h y d ro g e n b o n d in g a n d in c r e a s e d fre e N -H ; th a t is , l e s s e n e rg y w ould b e r e ­
q u ire d fo r t h e s e d e fo rm a tio n s in a n o n -h y d ro g e p b o n d e d c o m p o u n d . The
s h if t in a l l o f t h e s e p e a k s w ag s m a ll a n d th e %/N-?H p e a k w a s s t i l l fa r
e n o u g h from 3400 cm - -*-.to s u g g e s t so m e h y d ro g e n b o n d in g m ig h t s t i l l be in-*
v o lv e d . T he p o s itio n o f th e z/C = O p e a k in c r y s ta llin e (Z -p y rid o n e i s a g a in
in d ic a tiv e o f h y d ro g e n b o n d in g ; fre e Z^C=O p e a k n o rm a lly a p p e a rs a t h ig h e r
e n e r g ie s , > 1700 cm - *-. T h e re fo re , a
= O p e a k s h ift in d ic a te s a c h a n g e in
b o n d in g h a s o c c u rre d a t th e o x y g e n a to m . The fre q u e n c y o f a TrC =O vibra-n
tio n in co m p o u n d s w h e re th e o x y g e p is q o o rd in a te d to a n o th e r atom o r g ro u p
o f a to m s i s d e p e n d e n t u p o n th e m a s s o f th e c o o rd in a tin g gro u p , i . e . . a n ip c r e a s e d m a s s w ill lo w e r th e fre q u e n c y . T h erefo re, if CK-rpyridone is c o o rd in ­
a te d to a m e ta l io n th ro u g h th e c a rb o n y l o x y g e n , th e zrC ==Q p e a k w o u ld b e
e x p e c te d to s h if t to lo w e r fr e q u e n c ie s . S u ch -a s h ift w a s g e n e r a lly o b s e r v e d
fo r th e M C lg • I C 5H 5N O c o m p o u n d s . A b so rp tio n p e a k s a ro u n d 1600 cm \
h a v e b e e n a s s ig n e d to V rin g v ib r a tio n s a n d /SiN-H v ib r a tio n s (30). F u n d a v
m e n ta l rin g v ib r a tio n s s h o u ld n o t b e a f f e c te d b y c o o rd in a tio n to m e ta l io n ,
b u t th e
v ib ra tio n (in^-p la n e b an d ) o f c c-p y rid o n e w o u ld b e a f f e c t e d .
T he in te n s ity of th f s p e a k i s in c r e a s e d a n d s h ifte d to s lig h tly lo w e r fre ­
q u e n c ie s , w liich s u g g e s ts t h a t th e ./S N -H v ib ra tio n h a s b e c o m e l e s s h in ­
d e r e d . T h e se c h a n g e s in th e in fra re d a b s o r p tio n b a n d s s e e m e d to in d ic a te
th a t (% -pyridone w a s c o o rd in a tin g Ifo th e m etjal io n s th ro u g h th e o x y g e n a to m .
T he u ltr a v io le t a b s o r p tio n b a n d s o f th e mo no -<%- p y rid o n e c o m p le x e s
(T able V II, p a g e 21) a re in good a g re e m e n t w ith th o s e re p o rte d b y M a so n (40)
- 44 r
for. < Z -p y rid o n e;. A m ax1. 2 2 4 ,. 293 m jj. T h ere w a s a g e n e r a l d e c r e a s e , how -,
e v e r, in th e m o la r a b s o r p tiv itie s o f t h e s e b a n d s in th e c o m p le x e s . The 224
mpi b a n d (6.ma?c = 7230) a n d .293 m y b a n d s ( 6 m ax ^ 5890) h a v e b e e n a s s ig n e d
b y M a s o n a s c h a r a c te ris tic : TT-^-Tt* a n d 7) —r7T* c a rb o n y l e le c tr o n ic tr a n tiit i o n s . C o o rd in a tio n to a m e ta l io n g e n e r a lly d e c r e a s e s th e m o lar ab so rp -,
t i y i t i e s o f th e s e t r a n s i t i o n s .. T h e re fo re , th e u ltr a v io le t s p e c tr a o f th e
M C lg • I C 5H 5N O c o m p le x e s se e m e d to in d ic a te th e o x y g e n atom w a s c o ­
o rd in a te d to th e m e ta l i o n .
M o le c u la r w e ig h t d e te r m in a tio n s o f th e C u , Co a n d N i c o m p le x e s a re
r a th e r i n c o n c l u s i v e . The e b u llio s c o p ic r e s u l t s in d ic a te th e c o m p le x e s d i s ­
s o c ia te a t e le v a te d te m p e ra tu re s ; o s m o m e tric r e s u lts s u g g e s t th e c o m p le x e s
m ig h t.b e te tr a m e r ic o r e v e n .h ig h e r p o ly m e ric s p e c i e s .
X -ra y p o w d er d iff ra c tio n p a tte r n s c le a r ly in d ic a te d t h a t th e fo u r.co m ­
p le x e s h a v e s im ila r s tr u c tu r e s . T h e .d a ta l i s t e d in T ab le VI, p a g e 20, sh o w
t h a t th e Co, N i a n d M n c o m p le x e s a re is o m o rp h ic . The d a ta a ls o in d ic a te d
som e d if f e r e n c e s b e tw e e n th e C u c o m p le x a n d th e o th e r th re e c o m p le x e s .
H o w ev er, i t is c le a r t h a t th e s tru c tu re o f th e Cu c o m p le x is s im ila r to th e
o t h e r s . S in g le c r y s ta l x - r a y d iff ra c tio n d a ta in d ic a te d t h a t th e re is a c lo s e
r e la tio n s h ip b e tw e e n th e C u a n d C o c o m p o u n d s . The s tr u c tu r e o f th e Cu
com poud h a s b e e n d e te rm in e d from a tw o -d im e n s io n a l p ro je c tio n o f s in g le
c r y s ta l d a ta g a th e r e d a n d tr e a te d b y n o rm al c r y s ta llo g r a p h ic p r o c e d u r e s ,
The u n it c e l l d im e n s io n s o f th e C u co m p o u n d a re a = 9.93% , b = 9.94%,
c = 3.95% a n d y = 113.2°; th e s tru c tu re w ill be d i s c u s s e d in g re a te r d e ta i l
l a te r in th e t h e s i s . The u n it c e l l d im e n s io n s o f th e C o c o m p o u n d , a = 2 4.8%,
- 45 b = 1 6 .7 $ , c = 8 .7 $ , h a v e a ls o b e e n d e te rm in e d from s in g le c r y s ta l d a ta a n d
a th r e e - d im e n s io n a l a n a ly s is is now u n d e r w ay. The d im e n s io n s for th e Cu
a n d Co c o m p o u n d s a p p e a r q u ite d iff e r e n t; h o w ev er, th e y m ay b e r e la te d , a s
sh o w n in F ig u re 39, by th e fo llo w in g :
A = 2
B =
+ b^ - 2 a b c o s (180° - 2f)
i
+ b% - 2 a b c o s ^
C = 2c
The c a p it a l l e t t e r s r e p r e s e n t th e C o c o m p o u n d ; s m a ll l e t t e r s r e p r e s e n t th e
Cu com pound.
F ig u re 39.
U n it C e ll R e la tio n s h ip o f Cu an d Co C om p o u n d s
I sh o w s th e g e n e r a l s h a p e o f th e C u C lg * I C5H 5N O u n it c e ll; II , th e
C oC lg ' I C 5H 5N O u n it c e ll ; I I I , th e r e la tio n s h ip b e tw e e n I a n d II; th e th ir d
a x e s , c an d C, a re p e rp e n d ic u la r to th e p la n e o f th e p a p e r. S o lu tio n o f th e
e q u a tio n s by u s in g th e a p p ro p ria te C u v a lu e s , g iv e s A = 2 2 $ , B = 16.6$,
C = 8 $ . T h e s e v a lu e s a re r e a s o n a b ly c lo s e to th e o b s e r v e d v a lu e s for th e
C o c o m p o u n d . The o b s e r v e d v a lu e (8.7$) fo r th e c a x is in th e C o com pound
—
46“
i s a p p ro x im a te ly te n p e r c e n t lo n g e r th a n th e c a lc u la te d v a lu e . The in ­
c r e a s e d le n g th m ay be d u e to a d iff e r e n t m o le c u la r p a c k in g in th e c r y s ta l;
th a t is , th e m o le c u le s in th e C u co m p o u n d a re a ll o r ie n te d in th e sam e m an ­
n e r a n d n e s t o n e on to p o f th e o th e r. If th e m o le c u le s do n o t n e s t , o u t- o f ­
p la n e d is to r tio n s w ou ld re q u ire g r e a te r m o le c u la r s e p a r a tio n a n d th e re fo re a
la rg e r c r y s ta l a x i s . The in c r e a s e d le n g th o f th e a a x is c o m p a re d to th e c a l ­
c u la te d v a lu e i s a l s o th o u g h t to be a fu n c tio n o f th e m o le c u la r p a c k in g , b u t
is a s y e t n o t c o m p le te ly u n d e r s to o d . T h e s e r e la tio n s h ip s s tro n g ly s u g g e s t
th a t th e m o le c u la r u n it in th e tw o s tr u c tu r e s i s th e s a m e .
D ic h lo ro -m o n o -Q ^ p y rid o n e C o p p er(II)
Single cry sta l x -ra y diffraction data in d ica tes the structure of
CuClg • I C 5H 5NO is a s shown in Figure 40.
Figure 4 0 .
CuClg • I C 5H5NO Structure
The compound is d efin itely d im eric. The bridging chlorine atoms and the Cu
atoms are a ll in the same plane; the Cu-Cu d istan ce is approxim ately 3.23%,
- 47 Cu-Cl'*' d is ta n c e s a re a p p ro x im a te ly 2 . 2 The C u--C l^ d is ta n c e i s a p p ro x i­
m a te ly 1 .6 2 in p r o je c tio n . T h is d is ta n c e is m uch to o s h o rt an d m ay in d ic a te
th a t th is c h lo rin e atom is n o t in th e sam e p la n e . The C u -O d is ta n c e , in
p r o je c tio n , is a ls o to o s h o rt an d s u g g e s ts th a t th e o x y g e n ato m is n o t in th e
sam e p la n e . A d d itio n a l re fin e m e n t o f th e a v a ila b le d a ta is re q u ire d b e fo re
th e p o s itio n s o f C l^ a n d O a to m s a p d th e (Z -p y rid o n e rin g s c a n be d e te r ­
m in e d . The re fin e m e n t p r o c e s s is now in p r o g r e s s . W ith th e in fo rm a tio n a t
h a n d , i t a p p e a rs th e e n v iro n m e n t o f th e C u a to m s is p ro b a b ly sq u a re p la n a r
o r d is to r te d te t r a h e d r a l . The s tru c tu re of th e c o m p le x a s p r e s e n te d s u p p o rts
th e c o n c lu s io n d ra w n from in te r p r e ta tio n o f th e in fra re d a n d u ltrav io le t.-,
s p e q tra th a t < £-pyridone w a s b o n d ed th ro u g h th e o x y g e n a to m .
The m a g n e tic m om ent o f th e C u C o m p lex (1.93 B.M.) h a s .b e e n d e te r - .
te rm in e d a t 80° and. 2 9 S0K a n d a p p e a rs to b e te m p e ra tu re in d e p e n d e n t. A
fe w co m p o u n d s c o n ta in in g c h lo r in e - b r id g e d c o p p e r a to m s h a v e b e e n p re v i­
o u s ly id e n tif ie d a n d in v e s t i g a t e d . C sC u C lg (1.93 B.M.) h a s b e e n a s s ig n e d a
d is to r te d o c ta h e d r a l s tru c tu re by F ig g is a n d H a rris (41) a n d I^ c h lu e tte f-and
c o -w o rk e rs (42). F ig g is arid H a rris h a v e s u g g e s te d th a t m a g n etic, m om ents,
p f te tr a h e d r a l C u c o m p le x e s m igh t b e h ig h e r th a n th e m a g n e tic m om ents fpr.
s q u a re p la n a r C u c o m p le x e s . C ^gC uC l^. (2.00 B.M.) i s a d is tp rte d . te tr a h e d ­
ro n (41), J jt(N H 3) 4] [C u C l4] , k no w n to h a v e a sq u a re p la n a r stru c tu re - (43,
44), h a s a m a g n e tic m om ent o | 1.77 BiM. C u C l3 (1.75 B.M,), F ig u re 43, h a s
a n in fin ite , p la n a r, c h lo r in e - b r id g e d c h a in s tru c tu re (45). S u c c e s s iv e c h a in s
a re o f f s e t so th a t c h lo rin e a to m s in a d ja c e n t c h a in s f a ll a b o v e an d b e lo w
e a c h c o p p e r atom g iv in g a d is to r te d o c ta h e d r a l a rra n g e m e n t. It h a s b e e n
— 48
s u g g e s te d (46) th a t th e low er, m a g n e tic m om ent fo r C uC lg i s d u e to a supere x c h a n g e p a th w a y v ia b rid g in g c h lo rin e a to m s b e tw e e n c h a i n s . A d is to r te d .
te tr a h e d r a l s tru c tu re fo r C uC lg • IC 5 H 5 N O a p p e a rs to b e m ore p ro b a b le in ­
s te a d o f a s q u a re p la n a r s tru c tu re w h en th e s u g g e s tio n o f F ig g is an d H a rris
a n d th e m a g n e tic m om ents o f know n te tr a h e d r a l an d s q u a re p la n a r c h lo rin e
b rid g e d C u(II) c o m p o u n d s a re c o n s id e r e d . The x - r a y c r y s ta l d a ta in d ic a te s
th a t th e d im e rs a re s ta c k e d o n e on to p o f th e o th e r, g iv in g c h a in s o f Cu
I■
a to m s th u s e lim in a tin g th e p o s s ib il ity o f c h lo r in e - b r id g e s b e tw e e n la y e r s o f
d im e rs to form a n o c ta h e d r a l C u e n v iro n m e n t s im ila r to C u C lg . T h erefo re, a
J.ower m om ent i s n o t e x p e c te d fo r C uC l2 •. I C5H 5N O . ■S in c e th e re a re k n ow n
o c ta h e d r a l a n d te tr a h e d r a l c h lo r in e - b r id g e d C u(II) co p ip o u n d s w ith s im ila r,
m a g n e tic m o m en ts, i t i s n o t p o s s ib le a t th is tim e to a s s i g n e ith e r a d i s ­
to r te d o c ta h e d r a l o r te tr a h e d r a l s tru c tu re to C uC lg • IC 5 H 5 N O .
The v is ib le s p e c tr a (F ig u re s 1 2 - 1 4 , p a g e s 22, 23) o f C uC lg • IC 5 H 5 N Q
e x h ib it m axim a a t 450 m# (CHgON), 790 mju (HgO) a n d 880 mjj ,(C3H5OH).
S e v e ra l C u(II) c o m p o u n d s e x h ib it m axima, in th e s e re g io n s a s sh o w n in T a b le
XVI; th e f ir s t s e v e n c o m p o u n d s c o n ta in c h lo rin e -b rid g e d C u a to m s . O n th e
b a s i s o f th e v is ib le s p e c t r a , a d is to r te d te tr a h e d r a l s tr u c tu r e m ig h t b e
fa v o re d fo r C uC lg • IC 5 H 5 N O .
. D iffu s e r e f le c ta n c e s p e c tra h a v e b e e n u s e d to o b ta in a p p ro x im a te a b ­
s o rp tio n s p e c tr a o f s o lid s in th e v is ib le o r n e a r u ltr a v io le t r e g i o n s . The r e ­
f le c ta n c e a n d a b s o r p tio n s p e c tra a re n o t a lw a y s i d e n t i c a l , b u t p ro g re s s h a s
b e e n m ade in th e in te r p r e ta tio n o f r e f le c ta n c e s p e c t r a . The d iff u s e r e f l e c t ­
a n c e sp e c tru m o f C uC lg • I C5H 5N O (F igure 2 1 , p ag e 28) s h o w s a m axim um
T 49 T a b le XVI
V is ib le A b so rp tio n B ands of Some R e p r e s e n ta tiv e C u(II) C om pounds
C om pound o r S p e c ie s
A m ax mjj
A ssig n e d
C o n fig u ra tio n
R e fe re n c e
L i2 C u C l4
450
D i s t . te tr a h e d r a l
(47)
Li2 C u C l4
375
P la n a r
(47)
[C H 3C (N H 2 )2I C u C I4
450
T e tra h e d ra l
(48)
C s 2 C u C l4
405
D i s t . te tr a h e d r a l
(49)
(2 -C H 3- C 3H 4 N )2 C u C l2 a
746
804
■ D i s t . te tr a h e d r a l
(50)
C s C u C l3
408
D i s t . o c ta h e d r a l
(51)
[P t(N H 3) 4][C u C l4]
402
700
765
S q u are p la n a r
(44)
C u (C 6H 5N iN N iC 6H 5)2 13
667 .
525. .
■S q u are p la n a r
(52)
C u C l2 • I C 5H 5NOc
' 7 8 9 -7 9 0
4 3 0 -4 5 5
D i s t . te tr a h e d r a l
(12).
C u C l2 • I R - C 5H 4NOc
7 5 0 -8 0 0
'4 3 0 - 4 7 0
D i s t . te tr a h e d r a l
(12)
.
a 2 -m e th y lp y rid in e
^ d ia z o a m in o b e n z e n e
c p y r id in e - N - o x id e
in th e 4 2 5 -4 5 0 mpi r e g io n . R os (5 1 ).h a s fo u n d a m axim um "al; 408 mjj in th e
d iff u s e r e f le c ta n c e sp e c tru m o f C sC u C lg (d is to rte d o c t a h e d r a l ) .
C uC lg • I C5H 5N O (p y rid in e -N -o x id e ), F ig u re I , p a g e 3, h a s a d is to r te d
te tr a h e d r a l s tr u c tu r e . M uto an d J o n a s s e n (12), a s p r e v io u s ly m e n tio n e d ,
h a v e p re p a re d C u(II) co m p o u n d s w ith s u b s titu te d p y r id in e - N - o x id e l i g a n d s .
.
- 50 T hey h a v e fo u n d th a t th e d iff u s e r e f le c ta n c e s p e c tra o f th e com pounds: a s ­
su m ed to h a v e a d is to r te d te tr a h e d r a l s tr u c tu r e e x h ib it m axim a in th e 4 0 0 435 mju r e g io n . T h e re fo re , in v ie w o f th e d a ta p r e s e n te d b y Ros a n d J o h a s s e n , a d is to r te d te tr a h e d r a l s tru c tu re fo r C uC lg ' I C 5H 5N O a p p e a rs m ore
lik e ly th a n a d is to r te d o c ta h e d r a l s tr u c tu r e .
T he x - r a y s in g le c r y s ta l, d a ta c le a r ly in d ic a te t h a t th e r e is no lin k a g e
b e tw e e n C u a to m s in a d ja c e n t d im e rs a s in C uC lg c h a in s a n d th a t o n ly th e
n o n -b rid g in g c h lo rin e a to m s a p p e a r to f a ll o u t o f th e p la n e . A lthough o n ly a
c o m p le te th r e e - d im e n s io n a l x - r a y a n a l y s i s w ill, u n e q u iv o c a lly e s ta b lis h th e
s tr u c tu r e o f C uC l2 • I C 5H 5N O , i t a p p e a r s th a t a v a ila b le x - r a y , v is ib le s o ­
lu tio n a n d d iffu s e r e f le c ta n c e s p e c tr a l d a ta su p p o rt a d is to r te d te tr a h e d r a l
s tr u c tu r e for th is c o m p le x .
D ic h lo r o - m o n o - # - p y r id o n e C o b a lt(II)
T he s in g le c r y s ta l x - r a y d iffra c tio n , d a ta fo r the. C o c o m p le x h a v e n o t
re a c h e d th e s ta g e o f re fin e m e n t o f .th e C u c o m p o u n d , b u t som e c h a r a c te r is ­
t i c s of th e s tru c tu re o f th e Co com p o u n d a re k n o w n . S in c e th e u n it c e l l s o f
t h e s e tw o c o m p o u n d s a re r e la te d a s sh o w n in F ig u re 39, p a g e 45, th e Qo
co m pound i s p ro b a b ly a l s o a c h lo rin e b rid g e d d im er a n d is e x p e c te d to h a v e
a d is to r te d te tr a h e d r a l s tru c tu re -sinfular tp fh e t p ro p o s e d fo r th e C u co m ­
pound.
T he m a g n e tic m om ent o f th e C o co m p o u n d is 5.39 B .M . a t 2 9 8 °K .. The
c a lc u la te d s p in o n ly m a g n e tic m om ent fo r s p in fre e C o(II) i s 3.88 B.M.
The
room te m p e ra tu re m a g n e tic m om en ts fo r s e v e r a l know n C o (II) co m p o u n d s a re
sh o w n in T a b le XVII. It i s im m e d ia te ly o b v io u s th a t th e m a g n e tic m om ents
- 51 T a b le XVII
Room T e m p e ra tu re M a g n e tic M o m e n ts fo r C o(II) C om p o u n d s
A s s ig n e d
C o n f ig ,
C om pound
o r S p e c ie s
M a g n e tic
M om ent(B .M .)
R e fe re n c e
(NH4)2 C o(S O 4)2 • GH2O
O c ta h e d ra l
5.1
(53)
C o C l4=
O c ta h e d ra l
4.8-5.2
(54)
C o (C H 3C N )6++
O c ta h e d ra l
. 4.9-5.6
(55)
C o C l2 • Z(C H 3C 5^ N )
T e tra h e d ra l
4.8
C s 2C o C l4
T e tra h e d ra l
4.5
C o C l4=
T e tra h e d ra l-
4.69
(54)
C o C l4=
T e tra h e d ra l
4.6-4.9
(57)
CoX4" 2
T e tra h e d ra l
■ 4.3-4.8
(55)
C o C l2 • 2 ( 2 ,6D M P N O )3
T e tra h e d ra l
4.59
(58)
C 0C I2 • I d ip y rid y la m in e
T e tra h e d ra l
4.51
(59)
C 0 (phtha Io c ya n in e )
S q u are P la n a r
2.4
(53)
(56)
.
(53)
o f th e s e c o m p o u n d s a re q u ite d iffe re n t from th e c a lc u la te d s p in - o n ly v a lu e .
S pin o n ly v a lu e s a re c a lc u la te d from th e e x p r e s s io n (53):
B.M. = V4S (S+l)
S = to ta l s p in q u an tu m num ber
T h is e x p r e s s io n is d e riv e d from th e th e o ry fo r a fre e m e ta l io n (no e x te r n a l
p e rtu rb in g f ie ld s ) by o m ittin g o r b ita l a n g u la r m om entum a n d c o n s id e rin g o n ly
s p in a n g u la r m om entum o f th e e le c tr o n . E le c tro n s o c c u p y in g a n o rb ita l e x ­
h ib it b o th s p in a n g u la r m om entum a n d o r b ita l a n g u la r m o m eh tu m . An u n r
p a ire d e le c tr o n a lw a y s c o n tr ib u te s its s p in a n g u la r momentum) to th e .
- 52 m a g n e tic m om ent o f a n io n ; a n e le c tr o n m ay c o n trib u te i t s o r b ita l a n g u la r
m om entum to th e m a g n e tic m om ent if th e r e is a r o ta tio n s Ily e q u iv a le n t o rb i­
t a l th a t c a n a c c e p t th e e l e c t r o n . T h at is , th e P a u li e x c lu s io n p rin c ip le m u st
be o b e y e d ; no tw o e le c tr o n s w ith th e s$ m e s p in c a n o c c u p y th e sam e o rb i­
t a l . T h is m e a n s, th e re fo re , th a t th e r o ta tio n a lly e q u iv a le n t o r b ita l m ay be
u n o c c u p ie d o r if o c c u p ie d , th e e le c tr o n b e in g tr a n s f e r r e d m u s t b e o f o p p o ­
s ite s p in to th e e le c tr o n in t h e .o r b i t a l . I t h a s a ls o b e e n sh o w n th a t s p in - .
o rb it c o u p lin g c o n tr ib u te s to th e m a g n e tic m om ent o f a n io n (5 3 /5 7 ,5 8 ).
R u s s e ll- S a u n d e r s s p in - o r b it c o u p lin g i n c r e a s e s th e d e g e n e ra c y (num ber o f
r o ta tio n a lly e q u iv a le n t o r b ita ls ) o f th e e le c tr o n ic s t a t e s o f a n io n an d th is
a ls o c o n tr ib u te s to th e m a g n e tic m om ent o f th e .io n . The C o (II) co m p o u n d s
l i s t e d in T a b le XVII h a v e m a g n e tic m o m en ts g re a te r th a n th e c a lc u la te d
s p in o n ly v a lu e . T h is in d i c a t e s .t h a t sdrpe e le c tr o n s a re c o n trib u tin g th e ir
o r b ita l a n g u la r m om ents to th e m a g n e tic m o m en t. O rb ita l a n g u la r m om entum
c o n trib u tio n s a lo n e c a n n o t a c c o u n t fo r th e la rg e d iff e r e n c e s o b s e r v e d , a n d
s p in -o rb it c o u p lin g m u st a ls o be c o n trib u tin g to th e m a g n e tic m om ent of
t h e s e c o m p le x e s . It is o b v io u s from th e d a ta in T ab le XVII th a t o c ta h e d ra l
c o m p le x e s e x h ib it g r e a te r o rb if a l a n d /o r s p in - o r b it c o u p lin g c p n trib u tio n s to
th e m a g n e tic f o m e n t th a n e ith e r te tr a h e d r a l o r sq u a re p la n a r c o m p le x e s .
The m a g n e tic , m om ent o f C oC lg ' IC 5 H 5 N O i s h ig h e r th a n o b s e r v e d v a lu e s
for s e v e r a l o c ta h e d r a l.C o(II) c o m p le x e s . T he re a s o n fo r th e h ig h m oment,
re m a in s u n e x p la in e d . The m a g n e tic d a ta a p p e a rs to s u p p o rt a n o c ta h e d ra l
s tr u c tu r e for C oC lg • I C 5H 5N O r a th e r th a n a te tr a h e d r a l s tr u c t u r e .
- 53 I
L ib u s a n d U ru sk a (60) s ta t e th a t te tr a h e d r a l C o(II) co m p o u n d s e x h ib it
c h a r a c t e r i s t i c a b s o r p tio n b a n d s a t 576, 608 a n d 638 mju. The m o lar a b s o r p t i v i t i e s o f te tr a h e d r a l C o(II) a b s o r p tio n b a n d s a re g e n e r a lly la rg e r th a n 100.
I
The m o la r a b s o r p tiv itie s o f o c ta h e d r a l C o(II) a b s o r p tio n b a n d s a re g e n e r a lly
s m a lle r th a n 100. In a d d itio n , o c ta h e d r a l (C o(II) s p e c ie s g e n e r a lly e x h ib it
a lo w i n te n s ity b a n d a ro u n d 515 mpi th a t d o e s n o t a p p e a r w ith te tr a h e d r a l
C o(II) co m p o u n d s (60). T he c o n fig u ra tio n o f C o(II) io n s in s o lu tio n is d e ­
p e n d e n t u p o n th e c o o rd in a tin g s tre n g th (lig a n d fie ld s tre n g th ) o f th e s o lv e n t;
w e a k ly c o o rd in a tin g s o lv e n ts y ie ld te tr a h e d r a l s p e c ie s , s tro n g ly c o o rd in g t^
in g s o lv e n ts p ro d u c e o c ta h e d r a l s p e c ie s (T able XVIII). The a b s o r p tio n b a n d s
fo r s e v e r a l know n C o(II) c o m p o u n d s a re l i s t e d in T ab le X V III.
T a b le XVIII
V is ib le S o lu tio n S p e c tra o f Known C o(II) C o m p o u n d s
C om pound
o r S p e c ie s
C o C l4' 2
S o lv e n t
A m ax Hty4
C H 3N O 2
593, 613(sh), 635
C o C l4" 2
C o n f ig .
R e fe re n c e s
(54)
668, 693 '
T e tra h e d ra l
(57)
CoX4-Z
C H 3CN
680
T e tra h e d ra l
(55)
C o C l2
(C H 3) 2 CO
575, 6 3 0 (sh), 674
T e tra h e d ra l
(61)
C o C l2 ■2 C 5H 5N
C H C l3
579, 611, 63 8 -6 6 2
T e tra h e d ra l
(56) .
C o C l2
C 5H 5N
576, 608, 638
T e tra h e d ra l
(60)
570, 610
O c ta h e d ra l
(55)
C o (C H 3C N )64""1"
■C H 3CN
C o C l2
P20
465, 513
O c ta h e d ra l
(62)
C oBr2 • 2 R -C 5H 4 NO
C H 3OH
530, 6 0 0 (sh ), 620
O c ta h e d ra l
(58)
C o (C lO 4)2
H 2O
513
O c ta h e d ra l
(63)
(C H 3)2CO
512
O c ta h e d ra l
(63)
C 2 H 5OH
515
O c ta h e d ra l
(63)
- 54 C oC lg ° I C5H 5N O h a s a n a b s o r p tio n m axim um a t 638 nyut w ith s h o u l­
d e rs a t 575, 612, 655 a n d 665 mju in C gH ^O H ; m axim a a t 556, 590 an d 660'
mw w ith s h o u ld e r s a t 570, 610 an d 650 in C H g C N . The m o la r a b s o r p tiv itie s
fo r t h e s e b a n d s sh o w n in T a b le V III, p a g e 2 7, a re la rg e r th a n 100. The a b ­
s o rp tio n b a n d s fo r C oC lg • IC 5 H 5 N O a g re e r e a s o n a b ly w e ll w ith th o s e r e ­
p o rte d in T a b le XVIII f o r -te tra h e d ra l C o(II) com pounds, in s o lv e n ts w ith low
d ie le c tr ic c o n s t a n t s . The low in te n s ity b a n d a ro u n d 515 mp o b s e rv e d fo r
o c ta h e d r a l C o (II) co m p o u n d s is m is s in g in C oC lg ° I C 5H 5N O e le c tro n ic
s p e c t r a . T h e re fo re , o n th e b a s i s o f th e d a ta p r e s e n te d ,, i t a p p e a rs th a t s o ­
lu tio n s o f C oC lg • IC 5 H 5 N O in C H gC N a n d C gH gO H c o n ta in te tr a h e d r a l
C o(II) s p e c ie s „
The d iff u s e r e f le c ta n c e sp e c tru m o f C oC lg • I C gH gN O , F ig u re 22, p a g e
28, i s s im ila r to i t s s o lu tio n s p e c tr a . T he co m p le x h a s r e f le c ta n c e m axim a '
a t 450, 545, 585 a n d 62 0 nyj w ith a s h o u ld e r a t 520 myi. T he d iffu s e r e f l e c t ­
a n c e b a n d s fo r k n o w n C o(II) c o m p o u n d s a re show n in T a b le XIX. King (56)
h a s n o te d s im ila r itie s b e tw e e n r e f le c ta n c e a n d s o lu tio n s p e c tr a o f p y rid in e
c o m p o u n d s o f C o(II). J o n a s s e n , in c o n tra s t "to K ing, h a s n o te d m arkdd d if­
f e r e n c e s b e tw e e n r e f le c ta n c e a n d s o lu tio n s p e c t r a , b u t h e s u g g e s ts th a t
t h i s c a n be u s e d a s a n in d ic a tio n th a t th e com pound h a s a d iffe re n t c o n ­
fig u ra tio n in th e s o lid s ta t e th a n w h en in s o lu tio n (12). H o w ev er, King d i s ­
s o lv e d h is c o m p o u n d s in C H C lg a n d J o n a s s e n d is s o lv e d h is in CH gOH a n d
o th e r s o lv e n ts w ith h ig h d ie le c tr ic c o n s ta n ts an d c o o rd in a tin g s tr e n g th .
T h is s u g g e s ts th a t th e s tru c tu re o f a co m p o u n d in th e s o lid s ta t e m ig h t v e ry
w e ll r e ta in th a t s tr u c tu r e in a w e a k ly c o o rd in a tin g s o lv e n t . The c o m p le x e s
- 55 T a b le XIX
D iffu s e R e f le c ta n c e B ands o f Known C o(II) C o m p o u n d s
C om pound o r S p e c ie s
A m ax mjD
A s s ig n e d
C o n f ig .
R e fe re n c e s
C o C l2 • 2 H 2O
510, 620
O c ta h e d ra l
(64)
C o C l2 • 2 (C H 3- C 5H 4N)
5 8 5 (sh ), 615(sh), 637
T e tra h e d ra l
(56)
C o C l2 • 2 C 5H 5N '
513(sh), 52 6, 541, 620
B ridged
O c ta h e d ra l
(65)
C o C l:4 ~ (in fu s e d s a lts )
600, 637, 676
O c ta h e d ra l
(66)
C o C l4= (in fu s e d s a lts )
595, 650, 735
D is to rte d
O c ta h e d r a l
(66)
C o C l4= (in fu s e d s a lts )
630, 670, 700
D is to r te d
O c ta h e d r a l
(66)
C o C l2 • I d ip y rid y la m in e
541, 559, 606
T e tra h e d ra l
(59)
C o C l^ ~ (s in g le c r y s ta l
s p e c tra )
7 1 5 -5 8 9 re g io n
D is to rte d
T e tra h e d ra l
(65)
5 8 2 -5 0 0 re g io n
4 5 5 -4 1 5 re g io n
C o C l2 • I d ip y rid y la m in e a n d C o C l3 • 2 (C H 3- C 5H 4N) c o n ta in lig a n d s th a t a re ■
s im ila r to CL -p y r id o n e an d th e ir r e f le c ta n c e s p e c tra a g re e re a s o n a b ly w e ll
w ith th e C o C l2 • I C 5H 3NO s p e c tru m . A lso, F e rg u so n in d ic a te s th a t k now n
d is to r te d te tr a h e d r a l C o C l4= s p e c ie s e x h ib it a b s o rp tio n b a n d s in th re e d i s ­
t i n c t re g io n s o f th e sp e c tru m (Table:XIX). O c ta h e d ra l C o(II) s p e c ie s g e n e r­
a lly h a v e r e f le c ta n c e b a n d s a b o v e 600 mw w h ile te tr a h e d r a l C o (II) s p e c ie s
g e n e r a lly h a v e r e f le c ta n c e b a n d s b e lo w 600 mju. T h ere i s o p e n d is a g re e m e n t
in th e lite r a tu r e c o n c e rn in g in te r p r e ta tio n o f r e f le c ta n c e s p e c t r a , b u t in
v ie w .o f th e r e s u l t s re p o rte d by K in g , F e rg u s o n (67) a n d M . G oodgam e, it
- 56 a p p ea r s th e r e f le c t a n c e data su p p ort th e c o n c lu s io n th a t C oO lg • I C 5H 5N O
i s a te tr a h e d r a l c o m p o u n d .
. E x c e p t for th e m a g n e tic m o m en t, th e d a ta a s s e m b le d a p p e a r to s u p ­
p o rt th e te tr a h e d r a l s tru c tu re p ro p o s e d fo r C oC lg • I C 5H 5NO from x - r a y d if ­
f r a c tio n d a t a . The m a g n e tic m om ent i s h ig h e r th a n a n y o th e r re p o rte d m o­
m e n t fo r a te tr a h e d r a l C o(II) com p o u n d a n d a p p e a rs to fa v o r a n o c ta h e d ra l
s t r u c t u r e . H ow ever, th e u n d e rs ta n d in g o f o r b ita l a n g u la r m om entum an d
s p in - o r b it c o u p lin g c o n trib u tio n s to th e m a g n e tic -m o m e n t o f C o(II) com ­
p le x e s i s s t i l l v e ry in c o m p le te an d th e m a g n e tic m o m e n t, a lp n e , sh o u ld n o t
b e u s e d a s a c r ite r io n in a s s ig n m e n t o f c o n f ig u r a tio n s . The c o m p o site d a ta
in d ic a te t h a t C oC lg , I C 5H 5NO is p ro b a b ly a te tr a h e d r a l c o m p o u n d .
D ic h lo ro -m o n o -c b -p y rid o n e N ic k el(H )
. ■
_
"
T he x - r a y p o w d er d iff ra c tio n d a ta l i s t e d in T ab le VI, p a g e 2 0, in d ic a te
t h a t C oC lg • I CgH gN O a n d N iC l2 • I C 5H 5NO a re is o m o r p h ic . T h erefo re,
s in c e C oC lg ° I C 5H 5NO i s is o s tr u c t u r a l to C uC lg • I C 5H 5NO, th e Ni com ­
p o und is a ls o e x p e c te d to be a c h lo rin e b rid g e d d im er w ith a d is to r te d t e t r a ­
h e d ra l N i(II) e n v iro n m e n t.
The m a g n e tic m om ent o f th e N i c o m p le x (3.65 B.M .)' i s te m p e ra tu re d e ­
p e n d e n t. The m om ent e x h ib its a s te a d y in c r e a s e a s th e te m p e ra tu re ;s lo w ­
e re d (T able V, p a g e 2 0). T h is ty p e o f b e h a v io r is c h a r a c t e r i s t i c of te tra h e ^ - •
d r a I N i(II) c o m p o u n d s (68). The m a g n e tic m o m en ts of s e v e r a l N i(II) com ­
p o u n d s a re k n o w n a n d som e o f them a re l i s t e d in T a b le XX. King an d c o ­
w o rk e rs (56) a n d L ev er (68) s tg te th a t te tr a h e d r a l N i(II) c o m p le x e s h a v e
- 57 T a b le X%
M a g n e tic M o m en ts of Some N i(II) C o m p o u n d s
C om pound o r S p e c ie s
M a g n e tic
M om ent(B .M .)
A ss ig n e d
C o n fig u ra tio n
R e fe re n c e s
(NH4)2 N i(S O 4)2 • 6 H 2O
3.3
O c ta h e d ra l
(53)
N i(H 2O) 6++
2.9-3.2
O c ta h e d ra l
(54)
N i(N O 3)2 • 3 C 5H 5N
3.21
O c ta h e d ra l
(69)
N iC l2 • C 5H 5N
3.47
B ridged
O c ta h e d ra l
(70)
N iC l2 • 2 C 5H 5N
3.37
B ridged
O c ta h e d ra l
(56)
N iC l2 • 2 C 5H 5N
3.39
B ridged
O c ta h e d ra l
(70)
N i[tr e m m e ]|C l2
3.42
T rig o n al
B ipyram id
(71)
(E t4N )2 N iC l4
3.8
T e tra h e d ra l
(53)
N iC l4"
3.87 ■
• T e tra h e d ra l
(54)
NiC(CH3) 3N O j4 (CJ4)2 .
3.86
. T e tra h e d ra l
(72)
N iC l2 * 2 Q u in o lin e
3.54
T e tra h e d ra l
(73)
(BuPh2P )^ N iC l2
3.35.
T e tra h e d ra l
(74)
K2 N i(C N ) 4
O
S quare P la n a r
(53)
■
®2 -d im e th y l- a m in o e th y la m in e
^ b u ty l- d ip h e y lp h o s p h in e
m a g n e tic m o m en ts o f 3.3-4.2 B.M.
■
''
S q u are p la n a r N i(II) co m p o u n d s a re g e n ­
e r a lly d ia m a g n e tic ; th e re fo re , it a p p e a rs s a f e to e lim in a te a s q u a re p la n a r
c o n fig u ra tio n for th e cC-pyridone c o m p le x in v ie w .o f th e d a ta p r e s e n te d . The
d a ta a ls o in d ic a te th a t som e o c ta h e d r a l N i(H ) co m p o u n d s h a v e m a g n e tic m o­
m e n ts t h a t f a l l w ith in th e ra n g e q u o te d fo r te tr a h e d r a l N i(II) c o m p o u n d s.
- 58 ■H o w ev er, n o n e o f t h e s e co m p o u n d s h a v e m om en ts th a t are tem p eratu re d e ­
p e n d en t . T h erefore, th e m a g n e tic m om ent o f N iC lg • I C 5H 5N O su p p o rts th e
p r o p o se d te tr a h e d r a l s tr u c tu r e .
The s o lu tio n s p e c tr a o f th e N i c o m p le x sh o w a b s o r p tio n m axim a a t 385
a n d 700 (very bro ad ) rnw i n .HgO; 413 a n d 760 (v ery b ro ad ) mjuj in C gH gO H ;
412,1.600 and 675
in H C O N (C H 3)g . The lite r a tu r e c o n ta in s m any s tu d ie s
o f N i(II) c o m p o u n d s w h ic h h a v e u s e d e le c tr o n ic s p e c tra to h e lp d e te rm in e
■
m o le c u la r c o n fig u ra tio n (54, 60, 63, 6 9 -7 2 , 7 4 -7 7 ). The a b s o r p tio n b a n d s fo r
te tr a h e d r a l a n d o c ta h e d r a l N i(II) s p e c ie s o v e rla p to a la rg e e x te n t an d m ak e
a s s ig n m e n t o f a c o n fig u ra tio n d if f ic p l t. H ow ever, th e m o la r a b s o r p tiv itie s
o f o c ta h e d r a l N i(II) c o m p le x e s a re g e n e r a lly l e s s th a n 100, w h ile m o lar ab-*
a b s o r p tiv itie s o f te tr a h e d r a l N i(II) c o m p le x e s a re g e n e r a lly m ore th a n 100.
The m o la r a b s o r p tiv itie s fo r N iC lg , I C 5H 5NO sh o w n in T a b le V III, p a g e 27, ;
a re low , b u t th e m axim a a g re e w ith th o s e o b s e rv e d fo r b o th c o n f ig u r a tio n s .
The o b s e r v e d c o n fig u ra tio n for N i(H) s p e c ie s in s o lu tio n a l s o a p p e a r to be
d e p e n d e n t u p o n th e c o o rd in a tin g s tre n g th o f th e U gand and s o lv e n t.u s e d a s is
th e c a s e w ith C o(II), N iC lg . I CgHgNO is in s o lu b le in w e a k ly c o o rd in a tin g
s o lv e n ts (C 5H 5 , C H C lg , CHgNOg , d io x a n e ) w h ic h m a k es, i t d iff ic u lt to
c h e c k th e p o s s i b i l i t y th a t N iC lg - I CgH gN Q m ig h t y ie ld a s p e c if ic N i(II)
s p e c ie s in th is ty p e o f s o lv e n t . H o w ev er, in lig h t o f th e o b s e r v e d a b s o f p t i v i t i e s for N iC lg • I C gH gN O a b s o r p tio n b a n d s , th e re i s p ro b a b ly an o c ta ­
h e d ra l N i(II) s p e c ie s in s o lu tio n .
The <&-pyridone com pound h a s a b ro a d r e f le c ta n c e m axim um b e tw e e n
4 5 0 -4 7 0 mjm. ■Known o c ta h e d r a l an d te tr a h e d r a l Ni(II) c o m p o u n d s b o th h a v e
- 59 r e f le c ta n c e m axim a in th is re g io n p lu s a d d itio n a l m axim a on e ith e r s id e o f
th a t b a n d . S tu d ie s by A lle p an d c o -w o rk e rs (78) an d N e ls o n and- S h ep ard ;
(70) w ith N iC lg • X C 5H 5N y ie ld th e b e s t a g re e m e n t w ith th e QL-pyridone
.
b a n d , b u t th e ir r e f le c ta n c e s p e c tra e x h ib it s e v e r a l b a n d s b e tw e e n 3 5 0 - .
700 mju
(the lim it s o f t h is stu d y ). T heir co m p o u n d s h a v e b e e n a s s ig n e d d i s ­
to r te d o c ta h e d r a l s t r u c t u r e s . It sh o u ld be n o ted th a t th ere i s a d iffe r e n c e
b e tw e e n th e r e f le c t a n c e band and th e s o lu t io n b a n d s for th e (X -pyridone
com p ou n d s . H o w ev er, a s p r e v io u s ly m e n tio n e d , th is s u g g e s t s a, ch a n g e in
c o n fig u r a tio n w h en th e s o lid i s d i s s o lv e d and th e c h a n g e a p p ea r s to be d e ­
p e n d en t up on th e s o lv e n t u s e d . At b e s t , th e r e f le c t a n c e sp ectru m o f
N iC lg • I C 5H 5N O su p p o rts an o c ta h e d r a l stru ctu re but i s b y no m ea n s c o n ­
c lu s iv e .
The s o lu t io n and r e f le c t a n c e sp e c tr a o.f N iC lg -* I C 5H 5N O w h en co m ­
p ared w ith sp e c tr a o f k n ow n N i(II) co m p o u n d s o ffer l it t le a s s i s t a n c e in th e
a s s ig n m e n t o f a s p e c i f i c c o n fig u r a tio n fo r 'th e c o m p le x Th th e s o lid s t a t e ,.. .
A d d itio n a l in v e s t ig a t io n i s n e c e s s a r y b efo r e t h e s e sp e c tr a w ill b e n e fit th e
stu d y . On th e o th er h a n d , th e x - r a y d iffr a c tio n data and e s p e c i a l l y th e
■
m a g n e tic m om ent data b oth v e ry c le a r ly -s u p p o r t a. te tr a h e d r a l stru ctu re for
N iC lg • IC g H g N O in th e s o lid s t a t e .
D ic h lo r o -m o n o -(X -p y r id o n e M a n g a n e s e (II)
T etra h ed ra l s tr u c tu r e s h a v e b e e n p r o p o se d for th e C u , C o and N i
. 1V m em b ers o f th e M C lg • I CgH^NO s e r ie s prepared in t h is stu d y . The rem a in ­
in g m em ber o f th e s e r ie s , M nC lg • I C 5H 5N O , p rob ab ly a l s o h a s .a te tr a h e ­
d ral s tr u c tu r e .b e c a u s e x - r a y pow d er d iffr a c tio n data sh o w it to be
- 60 - ■
is o m o rp h ic to th e Co a n d N i c o m p o u n d s . I t , to o , is e x p e c te d to b e a
c h lo r in e - b r id g e d dim er.
The m a g n e tic m om ent o f th e M n c o m p le x (5.97 B .M .) i s v e ry c lo s e to
th e c a lc u la te d s p in - o n ly m om ent o f 5.9 B.M . for a s p in fre e M n(II) io n (53).
The m om ent o f th e c o m p le x is te m p e ra tu re in d e p e n d e n t a n d a p p e a rs to fo llo w
th e C u r ie - W e is s Law. Both o c ta h e d r a l Kg M n (SO 4)2 • 6 HgO a n d te tr a h e d r a l
[(C g H g )^ N ^ M n C l^ h a v e m a g n e tic m o m en ts o f 5.9 B.M . (53). T here w a s r e ­
c e n tly re p o rte d (79) a f iv e - c o o r d in a te M n(II) co m pound w ith a trig o n a l b i -
•
p y ram id s tru c tu re a n d a m a g n e tic m om ent o f 5.85 B.M. I t a p p e a rs ,' th e re fo re ,
s in c e t h e s e k n o w n v a lu e s a re so c lo s e , th a t m a g n e tic d a ta fo r M n(II) com ­
p o u n d s w ill n o t p e rm it d if f e r e n tia tio n b e tw e e n s p e c if ic s tr u c tu r a l c o n fig u ra ­
tio n s . The m a g n e tic m om ent o f M nC lg • I CgHgNO in d ic a te s o n ly th a t th e
c o m p le x c o n ta in s s p in f r e e 'M n(Il). io n s .
The d iff u s e r e f le c ta n c e sp e c tru m o f M nC lg • IC g H g N O h a s b an d m a x i­
ma a t 365, 455, a n d a v e ry b ro a d b a n d , 5 0 5 -5 6 0 nyu th a t a p p e a r s to be c e n ­
te r e d a ro u n d 530 mju. C o tto n a n d c o -w o rk e rs (80) h a v e re p o rte d d iffu s e r e ­
f le c ta n c e sp ectra- for th r e e M n(Il) co m p o u n d s th a t h a v e b e e n a s s ig n e d t e t r a ­
h e d r a l s t r u c t u r e s . T hey sh o w th a t th e r e f le c ta n c e m axim a a p p e a r in th re e
d is t i n c t r e g io n s : 3 6 0 -3 8 5 mju, 4 3 0 -4 5 5 mju, a n d 4 7 0 -4 8 0 mju. The trig o n a l
b ip y ra m id M n(II) com pound m e n tio n e d a b o v e h a s r e f le c ta n c e m axim a a t 371
a n d 435 mju. No s o lu tio n s p e c tr a w e re o b ta in e d fo r M nC lg • I CgHgNO in
t h i s stu d y , b u t it s h o u ld b e n o te d th a t te tr a h e d r a l M n C l^ " s o lu tio n s p e c tra
re p o rte d by F u rla n i a n d -F u rla n i (81) a re a lm o s t id e n tic a l to th e r e f le c ta n c e
s p e c tr a re p o rte d by C o tto n a n d c o - w o r k e r s . ■A llen an d c o -w o rk e rs (83) h a v e
- 61re p o rte d s o lu tio n a b s o r p tio n m axim a a t 540, 460 an d 430 mjj fo r c h lo rin e b rid g e d o c ta h e d r a l M n(II) c o m p o u n d s. The M n C l2 ° I C 5H 5NQ r e f le c ta n c e
d a ta a g r e e s r e a s o n a b ly w e ll,w ith in th e lim its o f th e stu d y , w ith th a t r e ­
p o rte d fo r k now n te tr a h e d r a l M n(II) co m p o u n d s an d se e m to su p p o rt a t e t r a ­
h e d ra l c o n fig u ra tio n r a th e r th a n a n o c ta h e d r a l c o n fig u ra tio n .
S o lu tio n s p e c tr a w e re n o t o b ta in e d fo r th e M n(II) c o m p le x b e c a u s e it
i s m uch l e s s s o lu b le in th e com m on s p e c tr a l s o lv e n ts th a n th e C u , Co an d
N i c o m p le x e s . The i n t e n s i t i e s o f th e M n(II) b a n d s, d - d tr a n s itio n s , g e n e r e r a lly o b s e r v e d in th e v is ib le a n d n e a r in fra re d re g io n s o f th e sp e c tru m a re
w e a k a n d th e b a n d s a re v e ry s h a r p . T h e s e tr a n s itio n s a re fo rb id d e n t r a n s i ­
tio n s fo r d e l e c t r o n s . T h a t is , th e y a re fo rb id d e n b y th e m u ltip lic ity (sp in )
a n d L a p o rte s e le c tio n r u le s for e le c tr o n ic t r a n s i t i o n s , M an y tr a n s itio n
m e ta l io n s a re id e n tif ie d by a b s o r p tio n b a n d s in th e v is ib le re g io n of th e
s p e c tru m w h ic h h a v e b e e n a ttr ib u te d to d - d t r a n s i t i o n s . T he L ap o rte s e l e c ­
tio n ru le s p e c if ic a lly fo rb id s su c h tr a n s itio n s for a fre e m e ta l io n , b u t a c o ­
o rd in a te d m e ta l io n u n d e rg o e s m ix in g o f.d a n d p o r b ita ls to a s u f f ic ie n t d e ­
g re e th a t now an a llo w e d d - ? p tr a n s itio n m ay o ccu r, b u t w ill be l e s s in ­
t e n s e th a n c o m p le te ly a llo w e d t r a n s i t i o n s . A s p in fo rb id d e n tr a n s itio n re-^
q u ire s a n e le c tr o n to c h a n g e its s p in w h e n i t e n te r s a n o r b ita l th a t is
a lr e a d y o c c u p ie d by a s in g le e l e c t r o n . S u ch a c h a n g e d e c r e a s e s th e m u lti­
p lic ity o f th e s ta te an d is th e re fo re fo rb id d e n . A M n(II) io n , s p in free, is
a lr e a d y a t i t s m axim um m u ltip lic ity . The b a n d s o b s e rv e d in M n(II) S o lu tio n
s p e c tr a an d d iffu s e r e f le c ta n c e s p e c tra a re p ro b a b ly s p in fo rb id d e n d - d ,
a llo w e d d -p , a n d /o r c h a rg e tr a n s f e r (lig a n d
m etal) t r a n s i t i o n s . The d - d
- 62 —
tr a n s itio n s g e n e r a lly o c c u t a t lo w e r e n e r g ie s th a n ' d - p o r c h a rg e tr a n s f e r
tr a n s itio n s , The d - d tr a n s itio n s o b s e r v e d fo r te tr a h e d r a l M n(II) co m p o u n d s
w o u ld b e m ore in te n s e th a n for o c ta h e d ra l co m p o u n d s b e c a u s e a c e n te r of
sym m etry, a s in a n o c ta h e d r a l c o m p le x , d e s tr o y s d - p o r b ita l m ix in g . If a
I
tr a n s itio n is w e a k , a m ore c o n c e n tr a te d s o lu tio n is re q u ire d -fo r e le c tr o n ic
s p e c tr a l a n a ly s is . The q u a n tity of th e M n c o m p le x w a s lim ite d so e x te n s iv e
e le c tr o n ic in v e s tig a tio n w a s h in d e r e d . A g a in , o n ly a s in g le c r y s ta l x - r a y
a n a ly s is w ill e x a c tly sh o w th e s tru c tu re o f M nC lg ° I C 5H 5NO, b u t th e d a ta
g a th e r e d to d a te in d ic a te i t is p ro b a b ly a te tr a h e d r a l com pound;.
D ic h lo ro -h -O L -p y rid o n e M e ta l(II) C o m p le x e s
The u ltr a v io le t s o lu tio n s p e c tra o f th e c o m p le x e s, C uC lg - 2. C 5H 5NO
a n d C oC lg • 3 C 5H 5NO, differ from t h a t o f free. O rp y fid o n e m uch a s do th o s e
fo r th e c o m p le x e s p r e v io u s ly d e s c r ib e d fo r th e M Clg • IC g H g JlO c o m p o u n d s.
The in fra re d s p e c tra o f t h e s e c o m p o u n d s sh o w n in F ig u re s 36 an d 37, p a g e s
39 an d 40, -a ls o sh o w b a n d a n d in te n s ity s h if ts s im ila r to th e c o m p le x e s j u s t
d i s c u s s e d ; T a b le XXI l i s t s th e in fra re d b a n d s for t h e s e c o m p le x e s , T h e re ­
fo re, th e CL-pyridone is p ro b a b ly b o n d e d th ro u g h th e o x y g e n qtom to th e
m e ta l io n in t h e s e c o m p le x e s a s w e ll.
.
'
'
T he x - r a y p o w d er d iff ra c tio n d a ta fo r th e s e c o m p le x e s sh o w n in T a b le
X I, p a g e 3 4 , in d ic a te d if f e r e n c e s in i n t e n s i t i e s an d 9 a n g le s w h en c o m p a re d
w ith th e p o w d e r d iff ra c tio n d a ta fo r C uC lg » I CgHgNO a n d C oC lg -IC g H g N O .
The p o w d e r d a ta s u g g e s t th a t C uC lg • 2 CgH gN O an d C oC lg - 3 CgHgNO h a v e
d iff e r e n t s tr u c tu r e s th a n C uC lg - I C gH gN O a n d C oC lg • I C g H g N O .
-
63
-
Table-XXI,
C uC lg ' 2 (X -pyridone a n d C oC lg • 3 C t-p y rld o n e In fra re d Bapds
M
V N -H
V-C=C
C u(II)
3225(m)
1 640 (s)
C o(II)
33 0 0 (s) . • 1680(s)
■Ring
F req .
(am ido N -H )
,6 N -H
j8 C -H
IfC -H
y N -H
1590(s)
159-0 (s)
1540(s)
1470(m) ■
1380(s)
12 80(m)
1160(s)
109 5 (m)
1005(m)
865(s)
7 8 0 (s)
72 0(s)
1635(s)
-1570(m)
1490(m)
1440(s)
1280(m)
1180(s)
1 1 1 0 (m)
1 0 1 0 (s)
885(s)
79 0 (s)
74 0 (s)
1635(s)
S = S t r o n g , m = medium
As p r e v io u s ly m e n tio n e d ,, no e ffo rt w a s m ade to d e te rm in e th e mole-c u la r w e ig h t o f t h e s e c o m p le x e s .
■D ic h lo ro -b is -C b -p y r id o n e -C o p p er(II)
. The d iffu s e r e f le c ta n c e sp e c tru m o f C uC lg • .2 C ^H ^N O sh o w n in F ig u re
3 4 , p a g e 38, d o e s n o t sh o w a n y d e fin ite m a x im a . A s h o u ld e r a p p e a rs a ro u n d
700 mju, b u t d a ta c o u ld n o t be o b ta in e d b e y o n d th is p o in t. T h erefo re, it a P 1p e a r s th e r e f le c ta n c e s p e c tru m d o e s n o t p ro v id e u s e f u l d a ta fo r a s s ig n m e n t
o f a s p e c if ic c o n fig u ra tio n to C u C l2 • 2 C 5H 5N O .
The v is ib le s o lu tio n s p e c tra o f C u C lg • -2 C 5H 5NO sh o w n in F ig u re s 29
a n d 30, p a g e 35, a re s im ila r to th o s e o f CdCilg • I C 5H 5NO; C uC lg -ZCgHgNO
m axim a a p p e a r a t 786 mju in HgO, 450 a n d 875 (very b road) mjj in .C H g C N .
The m o la r a b s o r p tiv itie s (T able X III, p a g e 37) o f th e C pC lg • 2 CgH gNO co m ­
p o u n d a re lo w e r th a n th o s e o b s e rv e d fo r C uC lg - I C 5H 5N O . The b an d
■— 64 —
a ro u n d 450 m,M h a s b e e n a s s ig n e d to b o th o c ta h e d r a l a n d te tr a h e d r a l C u(II)
s p e c ie s in s o lu tio n (47). H ow ever, th e d a ta in T ab le XVI, p a g e 49, in d ic a te
a b g n d in th is re g io n i s p ro b a b ly c h a r a c t e r i s t i c o f a te tr a h e d r a l r a th e r th a n
a n o c ta h e d r a l C u(II) s p e c ie s „ T h is b a n d h a s n o t b e e n o b s e r v e d in s tro n g ly
c o o rd in a tin g s o lv e n ts (47). The s o lu tio n s p e c tr a l d a ta fo r C uC lg • 2 C 5H 5NO
a re in a d e q u a te a n d m ore e x te n s iv e in v e s tig a tio n is n e c e s s a r y b e fo re a n a b ­
s o lu te a s s ig n m e n t o f a s p e c if ic c o n fig u ra tio n fo r th e C u(II) in s o lu tio n c a n
b e m a d e . The c o n fig u ra tio n in s o lu tio n , a s h a s b e e n p r e v io u s ly d i s c u s s e d ,
i s n o t a lw a y s in d ic a tiv e o f th e s o lid s t a t e c o n f ig u r a tio n .
The m a g n e tic m om ent o f th e b is-O L -p yrid on e -Copper(II) c o m p le x i s '
1.8 B .M . It i s te m p e ra tu re in d e p e n d e n t a n d a p p e a rs to fo llo w t h e . C u rie W e is s Law. T h is v a lu e is w ith in th e ra n g e o b s e rv e d fo r b o th te tr a h e d r a l a n d
o c ta h e d r a l C u(II) c o m p o u n d s . T h e re fo re , i t is n o t p o s s ib le to d e te rm in e from
th e m a g n e tic d a ta a lo n e th e c o n fig u ra tio n o f C uC lg • 2 C 5H 5N O .
■ ■
The c o m p o s ite d a ta a re n o t s u f f ic ie n t.to p ro p o s e a c o n fig u ra tio n fo r
C u C l2 • 2 C 5H 5NO in th e s o lid s t a t e . The lim its o f th e r e f le c ta n c e sp e c tru m
re q u ire e x te n s io n b e fo re th is in fo rm a tio n w ill be u s e f u l. A d d itio n a l s o lu tio n
s p e c tra in w e a k c o o rd in a tin g c o Iv e n ts w ill b e n e c e s s a r y b e fo re a s tru c tu re
■fo r C uC lg • 2 C 5H 5 c a n b e e s t a b l i s h e d .
D ich lo ro -tris-(% > -p y rid o n e C o b a lt(II)
The m a g n e tic m om ent o f th is co m p o u n d i s 4.85 B.M. a t room te m p e ra ­
tu re a n d is te m p e ra tu re in d e p e n d e n t. T h is v a lu e is w ith in th e ra n g e norm ­
a lly a c c e p te d for o c ta h e d r a l s p in - f r e e C o (II) c o m p o u n d s . M . G oodgam e h a s
— 65 —
p re p a re d o c ta h e d r a l d i i o d o - t r i s - (d ip y rid y la m ip e ) c o ha It (II) a n d re p o rte d a
m a g n e tic m om ent o f 4.94 B.M . (59). B ia g e tte a n d H a e n d le r (69) h a v e p re ­
p a re d C o(N O g )2 • 3 C 5H 5N a n d fo u n d i t s m a g n e tic m om ent to b e 4.60 B.M.
T h is com pound h a s a ls o b e e n a s s ig n e d a n o c ta h e d ra l c o n fig u ra tio n * B ertran d
a n d P ly m a le (83) h a v e p re p a re d te tr a h e d r a l C oC lg • 3 C 5H 5NQ (p y r id in e -N o x id e ) a n d fo u n d its m a g n e tic m om ent is 4.67 B.M. It a p p e a r s a s th o u g h a n
o c ta h e d r a l s tru c tu re i s fa v o re d for th e tris-C O -p y rid o n e c o m p le x , b u t a t e t r a ­
h e d ra l s tru c tu re c a n n o t b e ru le d o u t by m a g n e tic d a ta a l o n e .
The d iff u s e r e f le c ta n c e sp e c tru m sh o w n in F ig u re 3.5, p a g e 38, for
C oC lg * 3 C.5H 5NO h a s m axim a a t 4 5 0 (sh ), 515, 530 a n d 640 n y j. The o c ta ­
h e d ra l com pound p re p a re d by M . G oodgam e, m e n tio n e d a b o v e , h a s r e f le c t­
a n c e m axim a a t 4 2 1, 481 a n d 541 myJ. The o c ta h e d r a l co m p o u n d p re p a re d b y
B ia g e tti a n d H a e n d le r h a s r e f le c ta n c e m axim a a t 4 8 0 (sh ), 530 an d 625 mjui.
T h ere i s a ls o r e a s o n a b le a g re e m e n t b e tw e e n th e C oC lg ° 3 C 5H 5NO d a ta a n d
th e d a ta fo r k now n o c ta h e d r a l C o(II) c o m p o u n d s p r e s e n te d in T ab le XIX, p a g e
55, T h e re fo re , C oC lg • 3 C 5H 5NO i s p ro b a b ly a n o c ta h e d r a l c o m p o u n d .
The s o lu tio n s p e c tr a fo r C oC lg • 3 C 5H 5NO s h o w n .in F ig u re s 3 1 -3 3 ,
p a g e s 36 a n d 37,. a re a lm o s t id e n tic a l to th o s e o f C oC lg • I C 5H 5N O .
C oC lg • 3 C 5H 5NO s o lu tio n s , h o w ev er, e x h ib it m o lar a b s o r p tiv itie s c lo s e r to
th e 100 re g io n w h ic h is c h a r a c te r is tic o f o c ta h e d r a l C o(II) s p e c i e s . The
lo w e r m o la r a b s o r p tiv itie s , h o w e v er, do n o t fa v o r a n o c ta h e d r a l C o(II) s p e ­
c i e s w h en C oC lg • 3 C 5H 5NO is d i s s o l v e d . I n s te a d , i t a p p e a r s a s th o u g h
b o th c o m p le x e s form th e sam e C o(II) s p e c i e s in s o lu tio n w h ic h , o n th e
-
66
-
b a s i s o f th e C oC lg • I C 5H 5NO s o lu tio n d i s c u s s i o n , s u p p o rts a te tr a h e d r a l
C o(II) s p e c ie s in s o lu tio n .
The r e f le c ta n c e a n d m a g n e tic d a ta o f C oC lg ° 3 C 5H 5NO a p p e a rs to
s u p p o rt th e c o n c lu s io n d raw n from th e x - r a y p ow der d a ta th a t th e tw o
(X -pyridone c o b a l t (II) c o m p le x e s h a v e d iff e r e n t c o n f ig u r a tio n . The d a ta p r e / '
s e n te d fo r C oC lg • 3 C 5H 5NO s u g g e s ts th e c o m p le x is p ro b a b ly o c ta h e d r a l.
SUMMARY
S e v e ra l new c o m p o u n d s o f Q tp y rld o n e w ith th e d iv a le n t tr a n s itio n
m e ta l io n s , M n , Co, N i a n d C u h a v e b e e n p re p a re d b y m ix in g e th a n o l s o lu ­
tio n s o f a n h y d ro u s m e ta l (II) c h lo rid e s a n d Q tp y r id o n e . The re a c tio n i s r e p ­
r e s e n te d b y th e g e n e r a l e q u a tio n :
. M C l2 + n C 5H 5NO ^ 2
MCl 2 . %C 5H 5NO
C om p o u n d s w ith n = I h a v e b e e n p re p a re d fo r e a c h o f th e m e ta l io n s
u s e d . The co m p o u n d s p r e c ip ita te r e a d ily u p o n m ix in g . The C u an d C o co m ­
p o u n d s c a n be r e c r y s t a lli z e d an d p u rifie d from C 2H 5O H . T he N i an d M n
c o m p le x e s a re l e s s s o lu b le b u t m ay a ls o b e c r y s ta ll iz e d from C g H 5O H . A ll
fo u r c o m p o u n d s h a v e b e e n in v e s tig a te d b y X '-ray d if f r a c tio n , m a g n e tic s u s ­
c e p tib ility , u ltr a v io le t s o lu tio n s p e c t r a , s o lid an d s o lu tio n v is ib le s p e c tr a ,
in fra re d s p e c tr a a n d e le m e n ta l a n a ly s is t e c h n i q u e s . A p r o je c tio n of s in g le
c r y s ta l x - r a y d if f ra c tio n d a ta fo r C u C l2 0 I C 5H 5NO in d ic a te s th e com pound
is a c h lo r in e - b r id g e d dim er. The d im e rs a re s ta c k e d o n e o n to p o f th e o th e r,
g iv in g c h a in s o f Cu a to m s th ro u g h o u t th e s tr u c t u r e . The c o m p o s ite d a ta
s tro n g ly s u p p o rt a d is to r te d te tr a h e d r a l s tr u c tu r e fo r C u C l2 • I C 5H 5N O . The
u n it c e l l s o f C u C l2 • I C 5H 5NO an d C o C l2 • I C 5H 5NO a re c le a r ly r e la te d
a n d th e re fo re , th e C o co m pound is p ro b a b ly a c h lo r in e - b r id g e d dim er, to o .
The d a ta o b ta in e d a ls o su p p o rt a d is to r te d te tr a h e d r a l s tru c tu re for
C o C l2 • I C 5H 5N O . X -ra y p o w d er d if f r a c tio n d a ta sh o w th e Co, Ni a n d M n
c o m p le x e s a re is o m o rp h ic so th e Ni a n d M n c o m p le x e s a re p ro b a b ly a ls o
c h lo r in e - b r id g e d te tr a h e d r a l d im e rs . W h ile n o t u n e q u iv o c a l, th e c o m p o site
- 68 —
e v id e n c e p r e s e n te d for th e N i an d M n c o m p o u n d s a ls o s u p p o rts a te tr a h e d r a l
s tru c tu re for t h e s e tw o co m p o u n d s .
A Co co m pound in w h ic h n = 3 h a s b e e n p re p a re d a n d in v e s tig a te d in a
lik e m anner, b u t w ith o u t s in g le c r y s ta l x - r a y d if f r a c tio n ‘a n a ly s is „ X -ra y
p o w d er d if f r a c tio n d a ta in d ic a te th a t th is com pound i s d iff e r e n t s tr u c tu r a lly
from th e n = I Co c o m p o u n d , a s w o u ld b e e x p e c te d . The d a ta c o lle c te d a n d
re p o rte d a p p e a r to fa v o r a n o c ta h e d r a l s tru c tu re fo r th e n - 3 c o m p o u n d .
An n = 2 C u co m pound h a s a ls o b e e n p re p a re d a n d in v e s t ig a te d . The
d a ta c o lle c te d a re in a d e q u a te to su p p o rt a s p e c if ic c o n fig u ra tio n for th is
com pound.
APPENDIX A
The A ttem p ted P re p a ra tio n o f B is - a c e ta m id o Q o p p er(II)
EXPERIMENTAL PROCEDURES AND RESULTS
Purification o f Acetamide
Acetam ide u sed in th is study w as purified by recry sta lliza tio n from
CHgOH a s ou tlin ed by Wagner (84). The product appeared a s long white
n e e d le s which melt at 8 0 .5 °C . It w as a ls o exam ined by nitrogen and infra­
red a n a ly s is . Figure 41 represents an infrared spectrum of acetam id e. The
spectrum is very sim ilar to one published by Kutzelnigg and M ecke (85).
r — I— — r -
Tl----- 1----- V.*^'TT"f i n
Percent T
U ___I
Figure 4 1 .
Infrared Spectrum of Acetam ide
Nitrogen a n a ly se s y ield 23.3% nitrogen found again st 23.7% nitrogen c a lc u ­
la te d . The purified product w as stored in capped b o ttles over anhydrous
CaSO^.
71. P re p a ra tio n a n d I d e n tif ic a tio n o f Sodium A c e ta m id e Sodium a c e ta m id e w a s p re p a re d b y th e fo llo w in g r e a c tio n sch e m e :
Na + C 2 H 5OH —> Na®Et C ^ ' -C- - - -
2> Na®CH 3C O NH® + C 2 H 5OH
A th r e e - n e c k ro u n d b ottom f la s k w a s e q u ip p e d w ith a re flu x c o n d e n s e r,
p r e s s u r e - e q u a liz i n g d ro p p in g fu n n e l a n d n itro g e n g a s in le t.. The f la s k w a s
im m e rse d in a n ic e b a th a n d s tirre d m a g n e tic a lly . Sodium m e ta l w a s f r e s h ly
c u t in a g lo v e b a g to a p p ro x im a te ly o n e c u b ic c e n tim e te r c h u n k s ju s t b e fo re
u s e ; th e c h u n k s w ere p la c e d in a s m a ll s in g le - n e c k f la s k f it te d w ith a ru b ­
b e r s le e v e th a t c o u ld be c lo s e d w ith a s c re w c la m p . The so d iu m m e ta l w a s
a d d e d to th e r e a c tio n f la s k by s lid in g th e s le e v e o v e r a jo in t a n d in v e rtin g
th e f la s k c o n ta in in g th e so d iu m m e ta l. The re a c tio n f la s k w a s flu s h e d w ith
d ry n itro g e n for te n m in u te a b e fo re th e so d iu m m e ta l w a s a d d e d . The s y s te m
w a s c o n tin u o u s ly f lu s h e d w ith dry n itro g e n d u rin g th e r e a c tio n . A b so lu te
C 2H 5O H , d rie d by d i s t i l l a t i o n from M g tu rn in g s , w a s a d d e d s lo w ly th ro u g h
th e d ro p p in g fu n n e l to th e sodium m e ta l w ith s tir r in g . A p p ro x im ately 300 m l
o f C gH gO H w a s u s e d p e r m o le c u la r w e ig h t o f sodium m e ta l.. The re a c tio n
p ro c e e d s v e ry sm o o th ly u n d e r t h e s e c o n d itio n s . A fter d is a p p e a r a n c e o f th e
so d iu m m e ta l, th e m ix tu re w a s s tirre d fo r o n e hour w ith o u t th e ic e b a th . A
C 2H 5OH s o lu tio n o f a c e ta m id e Was th e n a d d e d d ro p w ise to th e r e a c tio n m ix­
tu re w ith s tir r i n g . F o llo w in g fin a l a d d itio n o f th e a c e ta m id e , th e m ix tu re
w a s w arm ed to a p p ro x im a te ly 6 O0 C a n d s tir r e d for o n e h o u r. The C 2H 5QH
w a s th e n re m o v e d by v a cu u m d is t i l l a t i o n a n d th e p ro d u c t w a s h e d w ith d ry
e th e r a n d d rie d in v a c u o o v e r KOH for 24 h o u r s . The p ro d u c t is a w h ite
- 72 h y g ro s c o p ic pow der. It w a s s to re d o v e r KOH or a n h y d ro u s C aS O ^ in tig h tly
c lo s e d b o t t l e s .
F ig u re 42 is a n in fra re d sp e c tru m o f so d iu m a c e ta m id e . The sp e c tru m
w a s d if f ic u lt to o b ta in b e c a u s e th e co m pound w a s h y g ro s c o p ic ; i t is e s s e n ­
P e rc e n t T
t i a l l y id e n tic a l to o n e p u b lis h e d by K u tz e ln ig g an d M e c k e (85). Sodium
F ig u re 42 . In fra re d S p ectru m o f Sodium A c etam id e
a c e ta m id e w a s a n a ly z e d for n itro g e n c o n te n t an d th e b a s e e q u iv a le n t in
w a te r w a s d e te rm in e d by s ta n d a rd a c id titrim e try . T y p ic a l r e s u lts a re l i s t e d
in T a b le XXII. S o lu b ility c h a r a c t e r i s t i c s o f sodium a c e ta m id e w ere d e te r ­
m in ed by p la c in g 10 mg o f so d iu m a c e ta m id e in I ml o f s o lv e n t a t room te m ­
p e ra tu re (e x c e p t for a c e ta m id e w h ic h w a s m o lte n ); th e m ix tu re s s to o d for
- 73 o n e h o u r b e fo re v is u a l e x a m in a tio n w a s u s e d t t i 'd e te rm in e s o lu b ility . The
r e s u l t s a re sh o w n in T a b le XXIII.
T a b le XXII
Sodium A c eta m id e A n a ly s e s
B ase E q u iv a le n t D e te rm in e d v s . S ta n d a rd H C l
T ria l
I
2
Found
C a lc .
0.963^0,02 3
I
%N
Found
C a lc .
. 0.992d:Q.007
I .
17.7+0.007
17.3
3
0.982^0.007
I '
' 16.4±0.29
17.3 .
T a b le XXIII
Sodium A c etam id e S o lu b ilitie s
S o lu b le
A ceta m id e
Amyl A lco h o l
E th y l A lc o h o l'
E th y le n e G ly c o l
Is o p ro p y l A lcohol
M e th y l A lcohol
P y rid in e
W a te r
P a r tia lly S o lu b le
D im e th y l s u lfo x id e
T e rtia ry B utyl A lco h o l
In s o lu b le .
A ceto n e
A c e to n itrile
B en z e n e
B is ( 2 -e th o x y e th y l)e th e r
C a rb o n T e tra c h lo rid e
C h lo ro fo rm .
D ie th y l E th er
D io x a n e
E th y l A c e ta te '
N ,N , D im e th y lfo m a m id e
A ttem p ted S y n th e s e s o f B is a c e ta m id o C o p p er(II) C o m p le x e s
D ire c t C o m b in a tio n
C o p p er(II) c a tio n i s a s tro n g L ew is a c id an d th e a c e ta m id o a n io n is a
s tro n g L ew is b a s e ; th e r e a c tio n :
-
N aC H 3CONH +. C u C l2
74
-
s o lv e n S N a C l + C u (C H s C O N H )2 • I s o lv e n t
w a s th u s a tte m p te d u n d e r a w id e v a r ie ty o f c o n d itio n s . N aC H 3 CONH a n d
a n h y d ro u s C u C l2 w e re d is s o lv e d in a com m on s o lv e n t o r d iff e r e n t s o l v e n t s .
M o la r r a tio s o f L C u (II):2 N aC H 3CONH w e re u s e d th ro u g h o u t. T h e se s o lu - •
tio n s w e re m ix ed in a r e a c tio n v e s s e l a n d s t i r r e d . Some s o lv e n ts g a v e a n
J
im m e d ia te p r e c ip ita te , b u t o th e rs re q u ire d p ro lo n g e d s tirrin g a n d /o r h e a tin g
b e fo re p r e c ip ita tio n o c c u r r e d . Some s o lv e n ts re q u ire d p a r tia l e v a p o ra tio n
b e fo re s o lid s fo rm e d . The s o lv e n ts l i s t e d in T ab le XXIV w e re u s e d in th e
a tte m p te d s y h t h e s e s .
T a b le XXIV
S o lv e n ts U se d in A tte m p te d S y n th e s e s
A ceta m id e
A c e tic a n h y d rid e
A ceto n e
A c e to n itrile
Amyl a lc o h o l
B en z e n e
B is - (2 - e th o x y eth yl) e th e r
B utyl a lc o h o l
C a rb o n te tr a c h lo r id e
C hlo ro fo rm
D ic h lo ro m e th a n e
D ie th y l e th e r
D im e th y ls u lfo x id e
D im eth y lfo rm am id e
D io x a n e
E th y la c e ta te
E th y l a lc o h o l
■E th y le n e g ly c o l
F orm am ide
G ly c e ro l
Is o a m y l a lc o h o l
Is o b u ty l a lc o h o l
Is o p ro p y l, a lc o h o l
M e th y l a lc o h o l
■P ro p y l a lc o h o l
P y rid in e
T e rtia ry b u ty l a lc o h o l
The s o lid s w e re s e p a r a te d b y f iltr a tio n an d a n a ly z e d to d e te rm in e
th e ir c o m p o s i tio n .■S o lv e n ts w e re e v a p o r a te d from th e f i l t r a t e s by h e a tin g
■
a n d /o r v a cu u m d i s t i l l a t i o n a n d th e r e s u ltin g r e s id u e s w e re a n a ly z e d . T a b le
XXV l i s t s th e r e s u l t s o f s e le c te d a tte m p ts .
To r e p la c e to t a l c o in c id e n t m ix in g o f th e r e a c ta n t s o lu tio n s , d rp p w is e
a d d itio n o f o n e r e a c ta n t s o lu tio n to th e o th e r w a s tr ie d in th e h o p e th a t th is
T a b l e XXV
R e s u lts o f S e le c te d B isa c e ta m id o C o p p er(II) • I. S o lv e n t S y n th e s is
Time
R eq u ired
fo r P p tn .
N a tu re
of
P ro d u c t
A c eto n e
+
i - p ro p y l a l e . 3
im m e d ia te
g re e n
am o rp h o u s
11.9
2 6.8
I ) S o lu b le o n ly in s tro n g a c id
A ceto n e
+
i - p ro p y l a l e . s
im m e d ia te
g re e n
a m o rp h o u s
46.7
26.8
2 )S o lu b le o n ly in s tro n g a c id
P y rid in e ^
im m e d ia te
brown. am o rp h o u s
—
24.5
1)1.R. sh o w s NH p re s e n t in o rig in a l
ppt; a b s e n t in s o lv e n t re s id u e
E th y len e
G ly c o l^
p ro lo n g e d
s tirrin g
b lu e
gummy
49.1
26.3
1)1. R. sh o w s NH a b s e n t in o rig in a l
p p t.
. 2 )D iffic u lt to o b ta in a w o rk ab le
s o lid
A cetam id eb
im m e d ia te
brow n
NHg e v o lu ­
tio n w ith p p t
fo rm atio n
S o lv e n t
%Cu
% Cu
F ou n d C a lc .
26.6
R em arks
1)
I.R . sh o w s NH a b s e n t in o rig in a l
p p t.
2)
A c etam id eb
im m e d ia te
b lu e - g r e e n
p o w d er
E th an o lb
im m e d ia te
b lu e p o w d er
28.1
b lu e p o w d e r0 62.1
28.1
1.9d)
26.6
E x trem ely in s o lu b le
. 1)
1.R. sh o w s NH a b s e n t in o rig in a l
re s id u e
2)
T urns brow n u p o n s ta n d in g
3)
0 r ig i n a l p p t e x tre m e ly in s o lu b le
I) Na C l e v id e n t in p ro d u c t; confirm ed
by x - r a y po w d er d iffra c tio n
2 )C 2N gO H w a sh s o lu tio n w as c o lo rs
a U p p e r s o lv e n t fo r C u C lg , lo w e r s o lv e n t fo f N aCH gC O N H
le s s
^C om m on s o lv e n t
c O rig in a l r e s id u e w a s h e d w ith C gH ^O H s e v e r a l tim e s to rem ove N a C l b e fo re a n a ly s is
^A ssu m in g C u (C H gO N H )g • I s o lv e n t
76 v a r ia tio n w o u ld s lo w th e r e a c tio n a n d p e rm it g r e a te r c o n tro l o f p ro d u c t fo r­
m a tio n . P r e c ip ita tio n o c c u rre d o r w a s in d u c e d a s p r e v io u s ly d e s c r ib e d . The
s o lid s w e re tr e a te d in th e sam e m a n n er w ith r e s u lts s im ila r to th o s e l i s t e d
in T a b le XXV.
A th ird g e n e r a l te c h n iq u e w a s p la c e m e n t o f b o th s o lid r e a c ta n ts in th e
r e a c tio n v e s s e l fo llo w e d by s o lv e n t a d d itio n a n d s t i r r i n g . S o lv e n ts w ere
c h o s e n to c o n tro l th e r e a c ta n t c o n c e n tr a tio n s in s o lu tio n a n d th e re fo re , c o n ­
tro l th e r a te o f p ro d u c t fo rm a tio n . The s o lid s o b ta in e d w e re a n a ly z e d a s b e ­
fo re w ith s im ila r r e s u l t s .
An e x p e c te d p r o d u c t, N a C l, o f th e r e a c tio n u n d e r in v e s tig a tio n w a s
o b ta in e d o n s e v e r a l o c c a s i o n s . Its p r e s e n c e w a s c o n firm e d b y x - r a y p o w d e r
d if f r a c tio n p h o to g ra p h s . The p r e s e n c e o f N a C l a s a n im p u rity ,in th e am o r­
p h o u s r e s id u e s w o u ld c e r ta in l y a f f e c t th e e le m e n ta l a n a l y s e s '. . Rem oyaI-o f
N a C l from th e r e s id u e s w a s a tte m p te d by w a s h in g th e r e s id u e s w ith
C 2 H 5OH . The w a s h in g s w e re q u a lita tiv e ly c h e c k e d fo r C f^ 1(AgNO3-),.and- N5 0 .
(flam e te s t ) . A fter s e v e r a l w a s h in g s , Na® a n d C 0 w e re n o t d e te c ta b le '!" The
r e s id u e s re m a in in g w e re n o t C u(C H gC O N H )2 - I s o lv e n t a s sh o w n in T ab le
XXV.
S o x h le t E x tra c tio n T e c h n iq u e s
N u c le o p h ilic 's u b s titu tio n is co m m o n ly u s e d in m any o rg a n ic s y n t h e s e s .
A n u c le o p h ilic r e a g e n t.( n u c le o p h ile ) is a n e le c tr o n d o n o r to a c e n tr a l a c ­
c e p to r a to m . A s tro n g n u c le o p h ile w ill g e n e r a lly re p la c e a w e a k e r n u c le o ­
p h i l e . T r a n s itio n m e ta l c o m p le x e s a ls o ta k e p a rt in n u c le o p h ilic
- 77 -
.■
s u b s titu tio n r e a c tio n s (86). L ig a n d s v a ry in e le c tro n d o n a tin g c h a r a c te r is ­
t i c s an d c o n s id e r a b le w ork h a s p ro v id e d a c l a s s i f i c a t i o n o f th e c o o rd in a tin g
s tr e n g th s o f th e m o st com m on lig a n d s (86). The a c e ta m id o a n d a c e ta te
a n io n s a re n u c le o p h ile s a n d L ew is b a s e s . A c e tic a c id h a s a pKa = 4.76 in
H gO ; 10.32 in e th a n o l (87). A cetam id e h a s a pKa = 15.1 in H gO ; pKa v a lu e s
in o th e r s o lv e n ts w e re n o t a v a i l a b l e , T h e s e pKa v a lu e s in d ic a te th e acet^a m id o a n io n i s a s tro n g e r n u c le o p h ile th a n th e a c e ta te a n io n . T h erefo re, th e
r e a c tio n :
C u (C H 3C O O )2 + 2 N a(C H 3CONH) s o lv e n t>
2 N a (CH3COO) + Cu(C H 3CONH)2 • I s o lv e n t
w a s c o n s id e r e d a s a n o th e r p o s s ib le s y n th e tic p ath w ay . C u (C H 3C O Q )2 (a.
b in u c le a r b id e n ta te co m p lex ) a p p e a re d to b e a good c o m p le x to u s e in s y n ­
t h e s i s o f C u (C H 3C O N H )2 • I s o lv e n t b y n u c le o p h ilic s u b s titu tio n 1. S e v e ra l
w o rk e rs h a v e u s e d s o x h le t e x tr a c tio n to p re p a re tr a n s itio n m e ta l c o m p le x e s
(89) so th e te c h n iq u e w a s u s e d in a tte m p te d s y n th e s e s o f
C u (C H 3C O N H )2 • I s o lv e n t by th e r e a c tio n j u s t sh o w n . A nydrous ■
C u (C H 3C O O )2 w a s p re p a re d a s d e s c r ib e d b y G rad d o n (90). H ere, too, a
v a r ie ty o f s o lv e n t s y s te m s w ere in v e s t i g a t e d . The r e a c t a n t s w ere a lte r n a te d
.b e tw e e n th e th im b le a n d s o lu tio n , b u t a lw a y s w ith th e sam e r e s u lts : bro w n
am o rp h o u s in s o lu b le s o lid s w ere p ro d u c e d .
S o x h le t e x tr a c tio n o ffe re d a n o th e r m e a n s of c o n tro llin g th e c o n ta c t
b e tw e e n th e r e a c ta n ts so i t w a s s u b s tit u te d for th e p re v io u s ly d e s c rib e d
te c h n i q u e s . The o rig in a l r e a c ta n ts , C u C l2 a n d N a (CH3CO NH ), w ere u s e d a s
w e ll a s a c e ta m id e a n d th e Pt b lu e in g r e d ie n ts (d e s c rib e d in n e x t s e c tio n ).
—78- ■
The r e a c ta n ts p o s itio n an d s o lv e n ts w e re v a rie d a s b e f o r e . As b e fo re , th e
p ro d u c ts o b ta in e d w e re n o t C u(C H gC C )N H ^ • I s o lv e n t a s sh o w n b y a n a ly ­
s e s . R e s u lts w e re s im ila r to th o s e o f e a r lie r a t t e m p t s .
In te rn a l H y d ro ly s is
O ne of th e f ir s t re c o rd e d r e a c tio n s o f a c o o rd in a te d o rg a n ic lig a n d
w a s th e h y d ro ly s is o f a c e to n itr ile c o o rd in a te d to p la tin u m (II) (91). G illa rd
a n d W ilk in s o n h a v e r e c e n tly (92) r e - e x a m in e d th is r e a c tio n a n d s u c c e s s ­
fu lly p re p a re d Pt(CH gC O N H )Z ' I HgO (P latin u m b lu e ). T h e y s u g g e s t th e
p la tin u m b lu e is form ed by th e h y d ro ly s is o f Pt(CH gC N )IzC lz th ro u g h th e
r e a c tio n :
P t(C H g C N )z C lz + 2 AgNOg: f 3„HzQ -—>
P t(C H sC O N H ) 2 • IH z O + 2 HNOg + 2 A gCl
The f iltr a te from th is r e a c tio n w a s a c id ic a n d th e pH o f th e f iltr a te (3.8) w a s
c lo s e to th e th e o r e tic a l v a lu e (3.7) e x p e c te d for th e m o la r q u a n titie s ' o f th e ­
re a c ta n ts u s e d . R e a c tio n o f p la tin u m b lu e w ith KCN g a v e a n o ra n g e s o lu tio n
w h ic h w a s r e p e a te d ly e x tr a c te d w ith e th e r. C o n c e n tra tio n o f th e d rie d
(NagSO^.) e th e r e x tr a c t g a v e w h ite c r y s ta ls , m e ltin g p o in t 3 2 °C , w h o se
in fra re d sp e c tru m w a s id e n tic a l w ith th a t o f a c e ta m id e . C h e m ic a l an d
s p e c tr o s c o p ic e v id e n c e b e s t fit a p o ly m e ric s tru c tu re in v o lv in g a c e ta m id o
b rid g e s , w ith w a te r m o le c u le s p ro b a b ly h y d ro g e n b o n d e d w ith in th e c r y s t a l .
T h is s u g g e s te d , th e re fo re , th a t p la tin u m b lu e m ig h t b e a b in u c le a r b id e n ta te
c o m p le x . The c o m p le x i s d ia m a g n e tic . P la tin u m b lu e , a s p r e s e n te d h e re ,
th e re fo re h a d som e o f th e c h a r a c t e r i s t i c s e x p e c te d fo r Cu(QHgCC)NH)z •! H zO .
79In v ie w o f t h e s e c h a r a c te r is tic s ,/ O u fC H g C N jg C lg w a s s u b s titu te d f o r .
P tfC H gC N jgC Ig to a tte m p t p re p a ra tio n o f C u (C H 3C O N H )2 • I HgO by th e r e ­
a c tio n j u s t d e s c r ib e d .. C u tC H g C N ^ C lg w a s p re p a re d b y s a tu r a tin g h o t
C H gC N w ith C uC lg a n d th e n c o o lin g th e m ix tu r e . C u(C H gC N )gC lg p r e c ip i­
ta te d a s a y e llo w -g o ld s o l i d . The C u(C H gC N )gC lg a n d AgNOg w ere in tr o ­
d u c e d in th e r e a c tio n sc h e m e in s o lu tio n a n d a s s p lid s in a v a r ie ty o f s o l­
v e n t s . In a l l c a s e s , A gC l form ed a n d w a s rem o v ed by f i l t r a t i o n . Thp f i l ­
t r a t e s w e re a n a ly z e d b e fo re a n d a f te r s o lv e n t e v a p o r a tio n . The f iltr a te s ■
w e re g re e n to b lu e - g r e e n in c o lo r a n d a n a ly s e s , in d ic a te d th a t Cu(N Q g)g w a s
th e d o m in a n t p ro d u c t.
.. C lo s e d . S y stem A ttem p ts
C o m pounds w h o se c o lo r, c r y s t a l l i n i t y an d a n a ly s e s e n c o u ra g e d fu rth e r
s tu d y g e n e r a lly tu rn e d brow n a f te r re m o v a l from. th e .r e a c tio n v e s s e l a n d /o r
upon a tte m p te d r e c r y s t a l l i z a t i o n . T h is d iff ic u lty s u g g e s te d th a t.th e co m Cpounds w e re r e a c tin g w ith Og o r HgO u p o n e x p o su re to th e a tm o s p h e re o r to
t r a c e s o f HgO p r e s e n t in th e r e c r y s t a lli z a tio n s o lv e n t. T h e re fo re , ‘a s y s te m
th a t w a s o x y g e n -fre e a n d u s e d a n h y d ro u s s o lv e n ts w a s c o n s id e r e d . The
te c h n iq u e p re v io u s ly d e s c r ib e d fo r th e p re p a ra tio n o f so d iu m a c e ta m id e (n i­
tro g e n a tm o s p h e re , d rie d , s o lv e n ts ) p ro v id e d s u c h a, c lo s e d s y s t e m . T h is
s y s te m w a s u s e d in a tte m p te d p re p a ra tio n s o f Cu.(CHgCONH)g • I s o lv e n t b y
o n e o f t h e s e tw o p a th w a y s :
I)
1
Na +. C 2H 5OH —> N a ^ C g H 5C P C H 3.? .9 .N? 2 .>
9 91^
C g H 5OH + N a® C H gC O N l P - ^
N ac i
4- C h(C H gC O N H )2' • IC gT l5OH
- 80 -r
2)
Na + C 2 H5OH
Na®C2 H5(^ >
N a C l + C u (C 2 H 5O )2 C H 3C Q N H 2^ Cjii(H H onO N H)2 - C 2 H 5OH
P ro d u c ts o f t h e s e r e a c tio n s w e re g re e n o r b lu e an d a m o rp h o u s . The s o lid s
w e re s e p a r a te d from th e r e a c tio n m ix tu re b y f iltr a tio n in a g lo v e b ag an d
d rie d in v a c u o b e fo re a n a l y s i s . R e s u lts a re lis t e d in T a b le XXVI w ith o th e r
c lo s e d s y s te m r e s u l t s .
T a b le XXVI
C lo s e d -S y s te m R e s u lts
T ria l
I
2
N i(C H 3C O N H )2 -C 2H 5OH
C u (C H 3C O N H )2 -C 2H 5OH
C u (C 6H 5C O N H )2 -C 2H 5O H
-Found 34.8% Cu 1.68%N
C a lc .. 28.2%
12.4 %
Found 56.6% C u
C a l c . 28.2%
1.31% N
10.5 % .
25.8% C u
18.2%
1.31% N
8. 0 0 %
29.0% C u
18.2% .
1.21% N
8.0 2%
■A tte m p te d -S y n th e s is o f B is a c e ta m id o N ic k e l(II) C om plex
T he p ro p e rtie s of th e C u(II) p ro d u c ts s u g g e s te d th e u s e o f a d ifferen ttr a n s itio n m e ta l io n to d e te rm in e if th e n a tu re o f th e m e ta l io n m ight b e a
c o n tro llin g f a c to r in p ro d u c t s ta b ility . Ba s o lo an d Peairson (86) in d ic a te t h a t
N i(II) c o m p le x e s a re m ore in e r t, g e n e r a lly , to n u c le o p h ilic ; a tta c k th a n -J
C u(II) c o m p le x e s . O rg e l (93) s u g g e s ts t h a t o c ta h e d r a l a n d te tr a h e d r a l N i(H )
c o m p le x e s a re m o r e .s ta b le th a n c o m p a ra b le Cu(IJ) c o m p le te s b e c a u s e o f
g r e a te r lig a n d f ie ld s ta b i liz a tio n .o f d® m e ta l i o n s . T h e re fo re , N iC l2 w a s
s u b s tit u te d fo r C u C l2 in th e a b o v e r e a c tio n sch e m e to s e e if
—
81
—
• N i(C H gC C )N H ^ • C gH gO H c o u ld be p r e p a r e d . The r e s u l t s w e re s im ila r to
th o s e o f C u(II), T a b le XXVI in c lu d e s th e n itro g e n a n a ly s is o f th e com pound .
re c o v e re d .
- A tte m p te d S y n th e s is o f B isb e n z a m id o C o p p er(II) C o m p lex
S u s p e c te d com pound d e co m p o sitio n , in th e p re v io u s C u(II) a tte m p ts
a ls o s u g g e s te d th e n e e d fo r a m ore s ta b le lig a n d . The a ro m a tic rin g w a s
c o n s id e r e d c a p a b le or p ro v id in g som e s ta b iliz a tio n ;
C u(C gH gC O O )g • C gH gO H i s th o u g h t to b e a b in u g le a r b id e n ta te co m p lex
(17, 94). B en zam id e w a s s u b s titu te d fo r a c e ta m id e in th e c lo s e d s y ste m to
s e e if C u (C gH gC O N H )g • I s o lv e n t q o u ld b e p ro d u c e d . R e s u lts s im ila r to
a c e ta m id e w e re o b ta in e d , a s sh o w n in T a b le XXVI;
.
DISCU SSIO N
The r e s u l t s sh o w n in T a b le XXV, p a g e 75, in d ic a te th e g e n e r a l n a tu re
o f th e d if f ic u l tie s e n c o u n te re d th ro u g h o u t th is p o rtio n o f th e stu d y . The p ro ­
d u c ts i s o l a t e d w e re b lu e , g re e n o r b ro w n ,. a m o rp h o u s, in s o lu b le s o l i d s .
E le m e n ta l a n a l y s e s o f t h e s e s o lid s in d ic a te d th a t C u tC H g C O N H ^ • I s o lv e n t
w a s n o t i s o l a t e d d u rin g th e stu d y . T a b le XXVII l i s t s som e c o m p o u n d s th a t
m ig h t h a v e b e e n .is o la te d a s r e a c tio n p r o d u c ts .
T a b le XXVII
S u s p e c te d R e a c tio n P ro d u c ts
C om pound
. C u (OH)2
CuCl 2
C uC lg ■ 4 s o lv e n t3
.C u C l2 • 2 C 5H 5N
C u(N O 3)2 • S H 2O .
C u (C H 3C O N H )2 • 2 s o lv e n t3
C u (C H 3C O N H )2 • 3 s o lv e n t3
C u(C H aC O N H )2 • 4 s o lv e n t3
C u (C H 3C O O )2 • I H2O
3 a c e to n e , is o p ro p y l a lc o h o l
N atu re
b lu e ,, am o rp h o u s p o w d er
t a n , am o rp h o u s p o w d er
? .
b lu e - g r e e n c r y s ta ls
b lu e p o w d er
?
'
'
?
?
b lu e - g r e e n c r y s ta ls
% Cu
65.5%.
47.0%
~ 1 7 .0 %
2 1.6 %
21.0%
~ 2 1.5%
'V l 8:0%
'M 5;o
31,6%
e th y le n e g ly c o l, a c e ta m id e
The in s o lu b ility o f th e co m p o u n d s in com m on n o n - p o la r s o lv e n ts w a s
so m e w h a t u n e x p e c te d . I t s e e m e d r e a s o n a b le to a s s u m e t h a t s u b s titu tio n o f
a n itro g e n ato m for a n o x y g e n atom in th e lig a n d w o u ld n o t d r a s tic a lly
c h a n g e th e s o lu b ility o f a n y p ro d u c ts o b ta in e d . H o w ev er, if th e a c e ta m id o
a n io n w a s c o n s id e r e d a s tro n g e r b a s e tha'n th e a c e ta te a n i o n ^ th e n th e b o n d
form ed b e tw e e n C u(II) a n d th e a c e ta m id o a n io n w ould b e m ore p o la r a n d th e
— 83 th e com pou nd w ou ld th e n be l e s s s o lu b le In n o n -p o la r s o l v e n t s . F o rm atio n
o f p o ly m e ric c o m p o u n d s m ig h t a ls o b e a r e a s o n fo r d e c r e a s e d s o lu b ility ,
C uC lg i s a p o ly m e ric c h a in a s sh o w n in F ig u re 4 3 .
Cu
'C u '
XX
x
I
''C u "
X XX
Cl "
F ig u re 4 3 .
The c h a in s a re in fin ite
X
C u;
X
"r C l
C uC lg S tru c tu re
an d th e c o p p e r a to m s sh o w s q u a re 4 - c o o r d in a tio n an d h a v e a s n e a r e s t
n e ig h b o rs , in a d ja c e n t c h a in s , tw o c h lo rin e a to m s (45). It m ig h t b e p o s s ib le
for th e a c e ta m id o group to form b rid g e s b e tw e e n th e c h a in s of C uC lg an d
form a l e s s s o lu b le p olym er; C uC lg is s o lu b le in C g H g O H . The d a ta c o l­
le c te d d u rin g th e s tu d y w e re in s u f f ic ie n t to id e n tify m o st o f th e r e a c tio n
p r o d u c ts . A few w e re id e n tif ie d a n d w ill be d i s c u s s e d .
W h en a lc o h o ls w ere u s e d in th e r e a c tio n sch e m e , th e p ro d u c ts w ere
s o lu b le o n ly in s tro n g a c i d . T h is s u g g e s te d a b a s ic c o p p e r(II) com pound
w a s p ro d u c e d . T h is r e a c tio n :
2 C H 3CONH g + 2 HgO
2 C H 3CONHg + 2 OH® C u ^
» C u(O H)2
c o u ld o c c u r if th e s o lv e n t h a s no t b e e n s u f f ic ie n tly d r ie d . Some o f th e r e ­
a c tio n p ro d u c ts d a rk e n e d d u rin g r e c r y s t a lli z a tio n an d p u r if ic a tio n a tte m p ts
- 84 w h ic h , a g a in , s u g g e s te d C u(O H )2 b e c a u s e it d e c o m p o s e s to g iv e CuO, a
b la c k p o w d er (45). X -ra y po w d er d iff ra c tio n p h o to g ra p h s in d ic a te d th a t CuO
w a s p r e s e n t in som e o f th e is o la te d p r o d u c ts .
R e a c tio n s y s te m s u s in g p y rid in e g e n e r a lly p ro d u c e d b lu e - g r e e n n e e d le
lik e c r y s t a l s from th e f il tr a te ; a brow n r e s id u e form ed im m e d ia te ly upon
m ix in g . The b lu e - g r e e n c r y s t a l s c o u ld b e r e c r y s t a lli z e d from p y rid in e .
V is ib le s o lu tio n s p e c tra o f th e r e c r y s t a lli z e d p ro d u c t g a v e a norm al c o p p e r
a b s o r p tio n b an d in th e 750 rryj re g io n , b u t d id n o t h a v e th e a b s o r p tio n b an d
a ttr ib u te d to d im e ric C u(II) co m p o u n d s a ro u n d 3 75 m^i(l). F ig u re 44 is a
v is ib le s p e c tru m o f th e b lu e - g r e e n c r y s t a l s .
F ig u re 44.
V is ib le A b so rp tio n S p e c tru m o f B lu e -G re e n C r y s ta ls from
C u C l2 • N aC H 3CONH • C 5H 5N S y ste m
The in fra re d s p e c tru m (F igure 45), h o w ev er, c le a r ly in d ic a te d th a t a c e ta m id e
w a s n o t p r e s e n t in th e c r y s t a l s . The c o p p e r c o n te n t o f th e c r y s ta ls
- 85 -
cm -1
F ig u re 4 5 .
In fra re d S pectru m o f B lu e -G re e n C r y s ta l s from
C u C l2 • N aC H 3CONH • C 5H 5N S y stem
a p p ro a c h e d th a t o f C u C l2 • 2 C 5H 5N (T ab le XXVI). T h e re fo re , fu rth e r i n v e s t i ­
g a tio n to id e n tify th e b lu e - g r e e n c r y s t a l s w a s u n d e rta k e n . H ot p y rid in e w a s
a lm o s t s a tu r a te d w ith C u C l2 a n d a llo w e d to c o o l; b lu e - g r e e n n e e d le - lik e
c r y s t a l s p r e c ip ita te d . T h e s e c r y s ta ls w e re c o m p ared (in fra re d s p e c tra a n d
x - r a y p o w d er d iff ra c tio n p h o to g ra p h s) w ith th e b lu e - g r e e n c r y s t a l s p re v i­
o u s ly o b ta in e d ; s p e c tra a n d p h o to g ra p h s for both s e t s o f c r y s t a l s w ere
i d e n t i c a l . F ig u re 46 is th e in fra re d sp e c tru m of th e c r y s t a l s p re p a re d from
C u C l2 an d C 5H 5N a lo n e ; F ig u re 47 is a n in fra re d s p e c tru m o f p y rid in e .
86
P e rc e n t T
-7 0 -
F ig u re 4 6 .
In fra re d S pectru m o f B lu e -G re e n C r y s ta l s from
P e rc e n t T
C uC lg • C 5H 5 N 'S y ste m
F ig u re 47.
In fra re d S p ectru m of P y rid in e
-
87
-
The in f r a r e d s p e c tru m o f th e o r ig i n a l bro w n r e s i d u e i n d i c a t e d th e p r e ­
s e n c e o f so d iu m a c e ta m id e , b u t i n s u f f i c i e n t d a ta w e re g a th e r e d to perm it
ab so lu te id e n tific a tio n .
A c e ta m id e h a s b e e n u s e d a s a n o n - a q u e o u s s o lv e n t b y Ja n d e r a n d
o t h e r s (88, 95, 96). It i s k n o w n to u n d e rg o a u t o p r o t o l y s i s w h e n m o lten :
2 CH 3 CONH 2
CH 3 CONH 0 + CH 3 C O N H fj
A m ides a re r e a d i l y h y d r o ly z e d u n d e r e i t h e r a c i d i c or b a s i c c o n d i t i o n s . N u­
c l e o p h i l i c a t t a c k of th e am id e o c c u r s w ith r e a s o n a b l e e a s e th ro u g h t h i s ty p e
r e a c t i o n (9 7):
/0
q
R—c (
O0
R—C—OH — > RCOO0 + NH3I
NH 2
NH2
W h e n m o lte n a c e ta m id e w a s u s e d a s th e s o l v e n t in t h i s s tu d y , ammonia g a s
w a s d e t e c t e d on a n u m ber of o c c a s i o n s : t h i s m e a n t a c e t a m i d e w a s b e in g
h y d r o l y z e d . M o lte n a c e t a m i d e i t s e l f r e l e a s e d no n o t i c e a b l e am m onia; th e
g a s form ed w h e n s o lid dodium a c e t a m i d e w a s a d d e d to th e m o lte n a c e ta m id e .
The fo llo w in g e q u a ti o n s m ig h t r e p r e s e n t a p a th w a y for p ro d u c in g NH3 from
th e r e a c t a n t s .
a)
2 CH 3 CONH 2 ^
b)
C H 3CO N h P
CH 3 CONH 0 + CH3C O N H p
Na C H 3C O N H ^
■ ■
(C H 3C O )2 NH + N H 3
R e a c tio n b) m ay p r o c e e d o n e s t e p fu rth e r -a cco rd in g to G ru ttn e r' (95):
. (C H 3C O )2 NH + N a C H 3CONH
» (CH3C O )2 N®Na® + C H 3C O N H 2
J a n d e r a n d W in k le r (88) h a v e u s e d m o lte n a c e ta m id e a s a s o lv e n t for
c o n d u c to m e tr ic t i t r a t i o n s o f h e a v y m e ta l a c e ta m id e c o m p le x e s w ith so d iu m
— 88 —
a c e t a m i d e . T hey c la im fo rm a tio n o f C u(C H gC C )N H ^ a n d
NagCCuX CHgCO N H )^ w h e n t i t r a t i n g C u C lg w ith so d iu m a c e t a m i d e in m o lte n
a c e t a m i d e . The c o m p o u n d s w e re n o t i s o l a t e d a n d a n a l y z e d . T hey sh o w t h a t
th d c o lo r o f th e r e a c t i o n m ix tu re c h a n g e s from g re e n — b l u e - g r e e n —>
b l a c k —f d a rk g re e n —> y e llo w —^ lig h t y ello w , a s t h e m o la r ra tio of
C u (II ):N a C H g C O NH i n c r e a s e s from 1:0
1.4. T hey do n o t i n d i c a t e a t w h a t
in o lar c o n c e n t r a t i o n of so d iu m a c e ta m id e th e c o lo r s c h a n g e or if th e c h a n g e
i s a b ru p t o r g r a d u a l . No m e n tio n w a s m ad e o f am m onia g a s r e l e a s e d u rin g
t h e r e a c t i o n . The c o n c e n t r a t i o n of so d iu m a c e ta m id e in th e m o lte n a c e t a ­
m ide w a s o n ly 0.03 N , th e r e f o r e s u g g e s t i n g th e CHgCONH® c o n c e n tr a tio n
w a s d ilu te e n o u g h to p r e v e n t n o t i c e a b l e r e l e a s e of am m onia w h ic h m ig h t b e
a d riv in g fo rc e o f r e a c t i o n b). D ilu te s o l u t i o n s m ight p e rm it r e a c t i o n b e ­
tw e e n Cu(II) a n d CH^CONH® a n d p r e v e n t fo rm atio n of (CH g C O )g N®N,a®.
D u rin g th e p r e s e n t s tu d y , so d iu m a c e t a m i d e a n d C uC lg c o n c e n t r a t i o n s w e re
g r e a t e r t h a n 0.1 N; NHg w a s d e t e c t e d , w h ic h s u g g e s t e d t h e CHgCONH
w as
c o n s u m e d in th e p ro d u c tio n o f NHg a n d ,(CHgCO)gN®Na® The p ro d u c ts o f
t h e r e a c t i o n , th e re fo re , m ig h t be C u [(C H g C O )g N ]2 or •
N a g C u [(C H gC O )gN ]gC lg . The l a t t e r co m p o u n d c o n ta i n s 16.5% Cu a n d w o u ld
n o t e x h ib it a n N -H a b s o r p tio n in a n in fr a r e d s p e c tr u m . T h is com pound m ig h t
b e b l u e - g r e e n , w h ic h s u g g e s t e d . th g t t h e - b l u e - g r e e n p o w d e r o b ta in e d from
th e s e c o n d r e p o r te d m o lte n a c e ta m id e , r e a c t i o n (Table-XXV, p a g e 75) m ig h t bp
N a 2C u [(C H g C O )g N ]g C lg . Ifow ever, i n s u f f i c i e n t d a ta p r e v e n te d more d e f i ­
n ite id e n tific a tio n .
/
- 89 The r e s u l t s o f t h i s p o rtio n of th e s tu d y c l e a r l y i n d i c a t e d t h a t s y n t h e ­
s i s a n d i s o l a t i o n o f c o p p er(II) a c e ta m id e w a s more d if f ic u l t th a n i n i t i a l l y
a n t i c i p a t e d . V a ria tio n o f s o l v e n t s a n d m ix in g t e c h n i q u e s d id n o t change" th e
r e s u l t s . . A tte m p ts to i n c r e a s e p ro d u c t s t a b i l i t y r e s u l t e d in s im ila r d if f ic u l­
tie s.
W h y i s o l a t i o n o f C u(C H gC C )N H ^ • I s o l v e n t w a s n o t a c c o m p lis h e d r e ­
m a in s a n u n s o lv e d p ro b lem a n d d e s e r v e s a d d i t i o n a l i n v e s t i g a t i o n . This
s tu d y h a s e v o k e d th e fo llo w in g s u g g e s t i o n s for fu rth e r i n v e s t i g a t i o n :
I.
U s e d ilu te r e a c t a n t c o n c e n t r a t i o n s (C uC lg a n d N aC H gC O N H ) w ith m o l­
te n a c e ta m id e to s e e if th e c o m p o u n d s c la im e d b y J a n d e r a n d W in k le r
. c a n be i s o l a t e d a n d i d e n tif ie d ; c o n s i d e r th e p o s s i b i l i t i e s of d o u b le s a l t
fo rm atio n .
2.
An i n v e s t i g a t i o n o f t h e r e a c t i o n b e t w e e n m o lte n a c e ta m id e and. so d iu m
a c e t a m i d e ; i s o l a t i o n a n d i d e n t i f i c a t i o n of r e a c t i o n p r o d u c t s . Study t h e
k i n e t i c s o f th e r e a c t i o n to d e te rm in e if NHg s o lu b ility , C H g C O N H ^ •
c o n c e n t r a t i o n o f N a ® c o n c e n t r a t i o n a re c o n tro llin g f a c t o r s .
3.
P e rfo rm a n ce of th e r e a c t i o n u n d e r v a c u u m c o n d itio n s .
4.
In tr o d u c e g a s c h ro m a to g ra p h ic a n d m a s s s p e c t r o s c o p i c a n a l y t i c a l t e c h ­
n iq u e s to a id i d e n t i f i c a t i o n of i s o l a t e d p r o d u c t s .
5.
I n i t i a t e s tu d y to d e te r m in e if t h e a s y m m e try of th e a c e ta m id e , group
(C -N = 1.33%, C -O = 1.26%) m ig h t p r e v e n t s y n - s y n b i d e n t a t e b i n u c l e a r
c o o rd in a tio n .
6 . . S y n th e s is a n d i n v e s t i g a t i o n of t r a n s i t i o n m e ta l c o m p o u n d s w ith s u b s t i ­
tu te d a m id e s.
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.
i
MONTANA STA TE U NIV ERSITY LIBRA RIES
3 1762 10005642
I
f
D378
H814
cop. 2
Houk, C. C.
Complexes of ot— pyridone with
d ivalent transition metals
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