Synthesis and study of some new amidine transition metal complexes
by Leo Allan Bares
A thesis submitted to the Graduate Faculty in partial fulfillment of the requirements for the degree of
MASTER OF SCIENCE in Chemistry
Montana State University
© Copyright by Leo Allan Bares (1966)
Abstract:
The syntheses of five new amidine-transition metal complexes are reported. Three of these complexes,
acetamidinium tetrachlorocuprate, acetamidinium tetrachlorocobaltate and acetamidinium
trichloronickelate, appear to be analogous to the corresponding cesium complexes. Copper (II)
acetamidinate and copper (II) benzamidinate have also been prepared.
Solution and diffuse reflectance spectra have been determined for all five complexes. Magnetic data
have been obtained for the chlorocuprate, acetamidinate and benzamidinate. These data suggest
possible structures, but do not allow unequivocal structural conclusions. I-I^
SYNTHESIS AND STUDY OF SOME NEW AMIDINE
' TRANSITION METAL COMPLEXES
by
LEO ALLAN BARES
y.
A t h e s i s s u b m itte d to th e G ra d u a te F a c u lty in p a r tia l
fu lfillm e n t of th e re q u ire m e n ts fo r th e d e g re e
:
■-
MASTER OF SCIENCE
in
C h e m istry
A pproved:
H e a d , M a jo r D e p a rtm e n t
C h a irm a n , E x am ining C o m m ittee
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
I
iii
ACKNOWLEDGEMENT .
T he a u th o r .g ra te fu lly - a c k n o w le d g e s th e a d v ic e a n d e n c o u ra g e m e n t
g iv e n by D r. K en n eth E m erso n d u rin g th e r e s e a r c h o n t h i s p r o je c t an d d u rin g
th e w ritin g o f th e t h e s i s .
A p p re c ia tio n i s e x p r e s s e d to th e U n ite d S ta te s D e p a rtm e n t o f H e a lth ,
E d u c a tio n , a n d W e lfa re fo r m ak in g g ra d u a te w ork p o s s ib le th ro u g h a n
N . D . E . A. F e llo w s h ip .
F in a lly , th e a u th o r w is h e s to th a n k h is p a r e n t s , Mr. a n d M rs. N o rb e rt
H . B a re s , fo r th e ir c o n tin u e d f a ith a n d e n c o u ra g e m e n t.
iv
TABLE OF CONTENTS
P ag e
LIST OF TABLES ............................. ..........................................................
LIST OF FIGURES
v
..................................................... .......................................................... v i
A B STR A C T............. ....................................................................................; ............................ v ii
IN T R O D U C T IO N ..........................................................................................
EXPERIMENTAL
P r e p a ra tio n of-S odium an d P o ta s s iu m Amide
. . . . . . . . . . . . . . .
6
A ttem p ts to P re p a re Sodium a n d P o ta s s iu m A c e ta m id in a te ....................
6
S y n th e s is o f A c eta m id in iu m C h l o r i d e .............................................
7
A tte m p ts to C o n v e rt A c etam id in iu m C h lo rid e to
Sodium A c e ta m id in a te
. N. .....................................................................
\8
S y n th e s is o f A c eta m id in iu m T e t r a c h l o r o m e t a l l a t e s ...........................
9
Preparation," o f A ceta m id in iu m T r ic h l o r o n ic k e la te ............................
17
S y n th e s is o f C o p p e r (II) A c e ta m id in a te .............................................. ...
S y n th e s is o f C o p p e r (II) B e n z a m id in a te
19
.................................• ....................22
D ISCU SSIO N
A ceta m id in iu m T e tra c h lo ro c u p ra te . . . . ; , ........................................................ 29
. A ceta m id in iu m T e tra c h lo ro c o b a lta te
......................................................
30
A c eta m id in iu m T r i c h l o r o n i c k e l a t e ............................................................
31
C o p p e r (il) A c e ta m id in a te a n d C o p p e r (II) B e n z a m id in a te
....................... 31
SUMMARY . . . , ............. ... . . ' ............................................................................................ 33
.LITERATURE CITED
. . ' .............................................................................................................34
V
LIST OF TABLES
P ag e
I
I.
S p e c tra l B ands a n d I n t e n s i t i e s o f A c etam id in iu m
T e tr a c h lo f o m e ta lla te s
.................................................
14
II.
M a g n e tic D a ta o n A c etam id in iu m T e tr a c h lo r o c u p r a te ......................
III.
S p e c tra l B ands a n d I n t e n s i t i e s o f C o p p e r(II) A m i d i n a t e s ....................... 27
IV. .
M a g n e tic D a ta o n C o p p er (II) A m i d i n a t e s ........................
16
28
vi
LIST OF FIGURES
P ag e
I.
B id e n ta te C o n fig u ra tio n s . . . . . . . . . . . . . . . . . . . .
................... .
2.
S tru c tu re o f C o p p er (II) A c e ta te M o n o h y d ra te . . . . . . . . . . . . . . .
2
3.
C o p p e r (II) F o rm ate T e tra h y d ra te
3
4.
U ltr a v io le t S p ectru m o f A c etam id in iu m T e tra c h lo ro c u p ra te
. . . . . .
12
'5.
V is ib le S p ectru m o f A ceta m id in iu m T e tra c h lo ro c u p ra te . . . . . . . . .
12
6.
U ltr a v io le t S p ectru m o f A c eta m id in iu m T e tra c h lo ro c o b a lta te
13
7.
V is ib le S p ectru m o f A ceta m id in iu m T e tr a c h lo r o c o b a l ta te ............. ...
8.
D iffu s e R e fle c ta n c e S p ectru m o f A cetam id in iu m
........................................................................
. . . . .
T e tra c h lo ro c u p ra te ..................................................................... ...................... ...
9.
I
13
15
D iffu se R e fle c ta n c e S p ectru m of A cetam id in iu m
T e tra c h lo ro c b b a lta te
............. ............................................. ......................... ; . • 15
10.
S o lu tio n S p ectru m o f A c eta m id in iu m T ric h lo ro n ic k e la te
. . . . . . . .
18
11 1
D iffu s e ,R e fle c ta n c e S p ectru m o f A cetam id in iu m
T ric h lo ro n ic k e la te . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
18
1 2 .,
U ltr a v io le t S p ectru m o f C o p p e r (II) A c e t a m i d i n a t e ............. ...
23
13.
V is ib le S p ectru m o f C o p p e r (II) A c e ta m id in a te
24
14.
R e fle c ta n c e S p ectru m o f C o p p er (II) A c e ta m id in a te
. . . . . . . . . . .
24
15.
In fra re d S p ectru m o f C o p p er (II) A c e ta m id in a te . . . . . . . . . . . . . .
25
16.
U ltr a v io le t S p ectru m of C o p p er (II) B e n z a m id in a te .................................... 25
17.
V is ib le S p e c tru m o f C o p p e r (II) B e n z a m id in a te ........................................... 26
18.
R e fle c ta n c e S p ectru m o f C o p p e r (II) B e n z a m id in a te
. . . . . . . . . . . . . .
............................. . 26
ABSTRACT
T he s y n th e s e s o f fiv e new a m id in e - tr a n s itio n m e ta l c o m p le x e s a re r e ­
p o rte d . T h ree of t h e s e c o m p le x e s , a c e ta m id in iu m te tr a c h lo r o c u p r a te ,
a c e ta m id in iu m te tr a c h lo r o c o b a lta te a n d a c e ta m id in iu m t r i c h lo r o n ic k e la te ,
a p p e a r to b e a n a lo g o u s to th e c o rre s p o n d in g c e s iu m c o m p le x e s . C o p p er (II)
a c e ta m id in a te a n d c o p p e r (II) b e n z a m id in a te h a v e a ls o b e e n p r e p a r e d .
S o lu tio n a n d d iff u s e r e f le c ta n c e s p e c tra h a v e b e e n d e te rm in e d for a ll
fiv e c o m p le x e s . M a g n e tic d a ta h a v e b e e n o b ta in e d for th e c h lo r o c u p r a te ,
a c e ta m id in a te a n d b e n z a m id in a te . T h e s e d a ta s u g g e s t p o s s ib le s t r u c t u r e s ,
b u t do n o t a llo w u n e q u iv o c a l s tr u c tu r a l c o n c lu s io n s .
INTRODUCTION
T he a b ility o f th e a c e t a t e a n io n to fu n c tio n a s e ith e r a m o n o d e n ta te o r
a b id e n ta te lig a n d (for w h ic h th e re e x is t th re e p o s s ib le c o n fig u ra tio n s a s
sh o w n in F ig u re I) in c o m p le x fo rm atio n w ith tr a n s itio n m e ta ls h a s b e en
d e m o n s tra te d (1 - 5 ) . C o m p le x e s s u c h a s c o p p e r (II) a c e ta te m o n o h y d ra te , in
w h ic h th e b id e n ta te n a tu re o f th e a c e t a t e a n io n h a s b e e n e s ta b lis h e d (2),
h a v e e v o k e d c o n s id e r a b le i n te r e s t in r e c e n t y e a r s . M uch e ffo rt h a s b e e n
e x p e n d e d in a tte m p tin g to e lu c id a te th e n a tu re of th e b o n d in g in v o lv e d in
th e s e c o m p le x e s , p a r tic u la r ly th e b o n d in g in v o lv e d in th e s y n - s y n b id e n ta te
c o m p le x e s .
S y n -A n ti
F ig u re I .
S y n -S y n
A n ti-A n ti
B id e n ta te C o n fig u ra tio n s
The s tru c tu re o f c o p p e r (II) a c e ta te m o n o h y d rate h a s b e e n d e te rm in e d
c r y s ta llo g r a p h ic a lly (2 ). The c o m p le x is d im e ric an d h a s a s tru c tu re in
w h ic h th e C u -C u d is ta n c e is 2 .6 4 % (o n ly s lig h tly g re a te r th a n th e C u -C u
d is ta n c e o f 2.56% in m e ta llic c o p p e r ) , th e C u -O d is ta n c e is 1.97% , a n d Cu
i s d is to r te d o u t o f th e CuO^ p la n e b y 0.22% .
C o p p er (II) a c e ta te m o n o h y d ra te e x h ib its a n a n o m a lo u s ly low m a g n e tic
m om ent o f 1.42 Bohr M a g n e to n s (co m p ared to th e s p in - o n ly v a lu e of
2
HgO
V
-
I
^ o \
CuC^
H 1C - 0 O
-O
^CH g
OHg
F ig u re 2 .
S tru c tu re o f C o p p er (II) A c e ta te M o n o h y d ra te
1.73 B. M . n o rm a lly o b s e r v e d for Cu (II) co m p o u n d s) a t room te m p e ra tu re an d
a ls o d is p la y s a n a b n o rm a l m a g n e tic s u s c e p tib ility v e rs u s te m p e ra tu re c u rv e
(6 ). R ath er th a n d e c r e a s in g w ith in c r e a s in g te m p e r a tu r e , a s w o u ld be p re ­
d ic te d by th e C u r ie - W e is s la w , th e s u s c e p tib ility i n c r e a s e s w ith in c re a s in g
te m p e ra tu re up to a b o u t room te m p e r a tu r e . At th is p o in t th e s u s c e p tib ility
b e g in s to d e c r e a s e . A d e fin ite m axim um in th e s u s c e p tib ility c u r v e , in d i­
c a tin g a n tife rro m a g n e tic b e h a v io r , is re a c h e d b e fo re a d h e re n c e to th e
C u r ie - W e is s la w b e g in s . T h is m axim um a llo w s o n e to c a lc u la te a m a g n e tic
e x c h a n g e e n e rg y b e tw e e n c o p p e r i o n s . The fo rm atio n of a v e ry w eak
S
b o n d b e tw e e n c o p p e r io n s form ed b y 3dx 2_y.2~^^x 2_y2 o r b ita l o v e rla p h a s
b e e n p o s tu la te d (6) to a c c o u n t for th e o b s e r v e d e x c h a n g e e n e r g y . P a ra m a g ­
n e tic re s o n a n c e sp e c tru m s tu d ie s (7) a n d a m o le c u la r o rb ita l c a lc u la tio n (8)
le n d su p p o rt to th is ty p e of d ir e c t e x c h a n g e in te r a c tio n h y p o th e s i s . A nother
d ir e c t e x c h a n g e in te r a c tio n p o s tu la te in v o lv in g th e fo rm a tio n o f a stro n g CT
b o n d form ed b y 3 d z 2 - 3 d z 2 o r b ita l o v e rla p h a s a ls o b e e n a d v a n c e d (9 ). Al­
th o u g h th e form er e x p la n a tio n o f th e b o n d in g in v o lv e d in th e c o p p e r (II)
3
a c e t a t e d im er h a s th e m ore s u p p o r t, n e ith e r e x p la n a tio n s e e m s to be e n ­
tir e ly a d e q u a t e .
C o p p er (II) fo rm ate te t r a h y d r a t e , w h ic h a s s u m e s a n a n t i - a n t i c o n fig u ­
r a tio n (10), a ls o e x h ib its a n a n o m a lo u s ly lo w m a g n e tic m o m en t, h a v in g a
m om ent o f 1.64 B. M . (1 1 ).
OH2
OH2
OH2
OH2
F ig u re 3 .
C o p p er (II) F o rm ate T e tra h y d ra te
The lo n g d is ta n c e o f 5 .8 0 $ b e tw e e n c o p p e r io n s p re c lu d e s in v o k in g a
d ir e c t e x c h a n g e in te r a c tio n m e c h a n ism to e x p la in th is s tro n g e r-th a n -n o rm a l
m a g n e tic in te r a c t io n . A s u p e r e x c h a n g e v ia a it p a th w a y e s ta b lis h e d by th e
3d.
o r 3d
o r b ita ls o f th e c o p p e r io n a n d th e 2pm- o r b ita ls o f th e b rid g in g
yz
xz
"
fo rm ate g ro u p h a s b e e n s u g g e s te d to e x p la in th e o b s e r v e d in te r a c tio n (1 2 ).
A s im ila r p a th w a y m ay a ls o be c o n s tr u c te d fo r th e c o p p e r (II) a c e ta te dim er
a n d s u p e r - e x c h a n g e m ay th e n be c o n s id e r e d a s a p o s s ib le m e ch a n ism for i t s
in te r a c t io n . A c o m b in a tio n o f d ir e c t a n d s u p e r e x c h a n g e m ay a ls o be c o n ­
s id e r e d a s a p o s s ib le m e c h a n ism in th is c a s e . The p r e c is e n a tu re o f th e
m e ta l- m e ta l b o n d in th e s y n - s y n b id e n ta te c o m p le x e s , a s s u m in g o n e , in
f a c t , e x i s t s , re m a in s a n in te r e s tin g a n d u n s o lv e d p ro b le m . The p re s e n t
p ro je c t is p a rt o f a la rg e r program d e s ig n e d to h e lp s o lv e th i s p ro b le m .
4
I, S -D ip h e n y ltria z e n id o c o p p e r(I) h a s a s y n - s y n 'b id e n ta te s tru c tu re
v e ry s im ila r to th a t o f c o p p e r (II) a c e t a t e , b u t th e s tru c tu re o f th e Cu (II)
c o m p le x h a s n o t b e e n d e te rm in e d u n e q u iv o c a lly . It h a s b e e n a s s u m e d ,
.
h o w e v e r, th a t th e s tr u c tu r e i s a ls o a s y n - s y n d im er (13). 1 ,3 - D ip h e n y ltria z e n id o C u (II) h a s b e e n re p o rte d to b e d ia m a g n e tic a t room te m p e ra tu re (13).
P re s u m a b ly , in c r e a s e d m a g n e tic in te r a c tio n m ay b e due to o n e o f , o r a com ­
b in a tio n o f , a t l e a s t tw o f a c t o r s . A d e c r e a s e d m e ta l-m e ta l d is ta n c e w ould
a llo w m ore e x te n s iv e o r b ita l o v e rla p a n d c o n s e q u e n tly g r e a te r m a g n e tic in ­
te r a c ti o n w o u ld o c c u r . A m ore s tro n g ly e le c tr o n r e le a s in g lig a n d sh o u ld in ­
c r e a s e th e m e ta l o r b ita l e le c tr o n d e n s ity a n d th e re b y a ls o in c r e a s e th e
o r b ita l o v e rla p ..
T he p re p a ra tio n a n d s tu d y o f tr a n s itio n m e ta l c o m p le x e s e m p lo y in g l i ­
g a n d s o th e r th a n , b u t g e o m e tric a lly s im ila r t o , a c e ta te m ay w e ll p ro v id e
in fo rm a tio n in u n d e rs ta n d in g th e n a tu re o f th e m e ta l- m e ta l b o n d in g in c o p r
■
per(II) a c e ta te a n d th e c o m p le x e s w h ic h e x h ib it s im ila r , a b n o rm a l m a g n e tic
p r o p e r tie s . It m ay b e p o s s ib le to s y n th e s iz e a s e r ie s o f s y n - s y n b id e n ta te
d im e rs w h ic h h a v e s tr u c tu r e s in te rm e d ia te to copper(II) a c e ta te a n d 1 ,3 -D i­
p h e n y l tr ia z e n id o c o p p e r (I I ) . For e x a m p le , th e s u b s titu tio n o f n itro g e n fo r
on© a c e t a t e o x y g e n a n d th e n s u b s titu tio n o f n itro g e n fo r b o th o x y g e n s 'w o u ld ,
p ro v id e s u c h a s e r i e s ; A s e r i e s o f th is ty p e sh o u ld p ro v id e m a g n e tic in fo r­
m a tio n w h ic h w o u ld a u g m e n t u n d e rs ta n d in g o f th e m a g n e tic in te r a c tio n s a n d
m e ta l- to - m e ta l b o n d in g in t h e s e c o m p o u n d s.
T he a m id in e s , w h ic h a re n itro g e n a n a lo g s to th e a l k a n o a t e s , h a v e
b e e n s e le c te d a s o n e ty p e o f lig a n d to em p lo y in th is e f f o r t. I t i s th e
5
p u rp o s e o f th e p r e s e n t w ork to s y n t h e s i z e , in p a r tic u la r , C u (II) a c e ta m id in a te a n d to perform p re lim in a ry in v e s tig a tio n o f th e c o m p le x .
EXPERIMENTAL
P re p a ra tio n o f Sodium a n d P o ta s s iu m Amide
P o ta s s iu m o r sodium a m id e c a n be p re p a re d by th e a c tio n o f p o ta s s iu m
o r sodium m e ta l on liq u id am m onia u s in g fe rric n itr a te h e x a h y d ra te a s th e
c a t a l y s t (14):
M (M =K o r Na) + N H 3 (I)
F e(N O 3) 3 • 6 H 2O
I
M NH2 + 2 H 2 .
T he p ro c e d u re fo llo w e d in th e a b o v e p re p a ra tio n s is e s s e n t i a l l y th a t of
G re e n le e a n d H en n e (14) w ith th e e x c e p tio n th a t a d d itio n a l d ry in g p re c a u ­
tio n s w ere o b s e r v e d . D rying w a s e ff e c te d b y w ith d ra w in g liq u id am m onia
from a n in v e rte d c o m m e rc ia l c y lin d e r in to a la rg e (3 -5 lite r) th r e e - n e c k e d
f l a s k , w h ic h w a s in s u la te d a n d h a d o n e n e c k fitte d w ith a tw o -f o o t d ry in g
tu b e to be a tta c h e d la te r to a re a c tio n f l a s k . W h en th e f la s k w a s h a lf - f ille d
w ith liq u id am m onia , fiv e to f if te e n g ra m s o f c u t sodium m e ta l w ere in tro ­
d u c e d th ro u g h th e th ird n e c k . A fter th e am m onia h a d b e e n in c o n ta c t w ith
th e sodium m e ta l for fiv e to e ig h t h o u r s , it w a s p a s s e d th ro u g h th e d ry in g
tu b e c o n ta in in g KOH in to a o n e - l i t e r r e a c tio n f la s k w h ere it w a s c o n d e n s e d
by a dry i c e - a c e t o n e c o n d e n s e r . The p ro c e d u re d e s c r ib e d b y G re e n le e an d
H e n n e w a s th e n a d h e re d to c l o s e l y .
A ttem p ts to P re p a re Sodium a n d P o ta s s iu m A c e ta m id in a te
C o rn e ll (15) d e s c r ib e s th e p re p a ra tio n o f th e so d iu m a n d p o ta ss iu m
s a l t s o f a c e ta m id in e by th e r e a c tio n b e tw e e n sodium or p o ta s s iu m am ide a n d
a c e to n itr ile in liq u id am m onia:
7
R e a c tio n s em p lo y in g b o th so d iu m a n d p o ta s s iu m w ere a tte m p te d s e v ­
e r a l tim e s w ith v a r ia tio n s in th e r a te o f a d d itio n o f r e a c ta n ts a n d by r e v e r s ­
ing th e o rd e r o f a d d itio n . In v a ria b ly , th e p ro d u c t w a s a re d d is h -b ro w n s o lid
w h ic h b e c a m e v e ry h a rd u p o n s ittin g a n d w h ic h w a s in s o lu b le in w a te r,
e th a n o l, a c e to n itr ile a n d d ilu te h y d ro c h lo ric a c i d . T h e s e o b s e r v a tio n s s u g ­
g e s t th a t c o n s id e r a b le p o ly m e riz a tio n o c c u r s r a th e r r e a d ily . The sodium
r e a c tio n s e e m s to be m ore s u s c e p tib le to p o ly m e riz a tio n th a n d o e s th e p o ­
ta s s iu m r e a c tio n . C o m m e rc ial so d iu m a m id e , w h ic h d o e s n o t see m to b e a s
r e a c tiv e a s th e so d iu m am id e p re p a re d b y th e m eth o d of H en n e a n d G re e n ­
l e e , g iv e s v e ry poor r e s u l t s in th e a b o v e a d d itio n . The l e s s e r r e a c tiv ity o f
th e c o m m e rc ia l so d iu m a m id e i s p ro b a b ly due to i t s lo w e r p u rity a n d to th e
f a c t th a t th e com pound is s h ip p e d u n d e r m in e ra l o i l , w h ic h is ra th e r d iff i­
c u lt to rem ove c o m p le te ly .
S y n th e s is o f A cetam id in iu m C h lo rid e
A c eta m id in iu m c h lo rid e is m o st c o n v e n ie n tly p re p a re d b y th e m ethod
o f P in n e r (16,17):
/O C 2 H 5
C H 3CN + C 2 H 5OH + H C l ------------- » C H 3C
NHo , C l
© ^ ©
/ G G 2H 3
G H 3C ^
NH2 , C l
©
0
/# 2
©
Id , C l
C H 3C x (©
NHr
C 2H 5OH
NH 3 »
ch^
f ( § 2. S
112
NH,
^N H 2
CHoC
, c?
<-----> CH2C
^ N H 9 , Cl
NHr
© ^ ©
D ry h y d ro g e n c h lo rid e g a s is p a s s e d in to a s o lu tio n o f a c e to n itr ile a n d e th ­
a n o l to form th e a c e tim id o e th y l e th e r h y d ro c h lo rid e , w h ich is th e n tr e a te d
V
8
w ith a n am m onia c a l- a lc o h o l s o lu tio n to form th e a c e ta m id in iu m c h lo rid e „
The y ie ld o f p u re a c e ta m id in iu m c h lo rid e a f te r tw o r e c r y s t a lli z a tio n s from
d rie d a b s o lu te e th a n o l is 65 to 70% o f th e th e o r e tic a l y i e l d .
T h ere e x i s t s a d is c r e p a n c y in th e lite r a tu r e o n th e m e ltin g p o in t o f
t h i s s u b s ta n c e . The H an d b o o k o f C h e m is try a n d P h y s ic s (18) l i s t s a m e ltin g
p o in t o f 1 6 6 -1 6 7 ° C for a c e ta m id in e . D ox (16) re p o rts a m e ltin g p o in t of
o f 1 6 4 -1 6 6 , P in n e r (17) r e p o rts 1 6 6 -1 6 7 , a n d L a n g e 's H a n d b o o k o f C h e m istry
(19) l i s t s a m e ltin g p o in t o f 177° fo r a c e ta m id in iu m c h lo rid e
H am m ond an d
N eum an (20) g iv e a m e ltin g p o in t o f 1 6 5 -1 6 8 ° fo r th e sam e c o m p o u n d . A ce­
ta m id in iu m c h lo rid e s y n th e s iz e d in th is la b o ra to ry m e lts a t 1 7 5 -1 7 6 ° a n d a
s a m p le .of th e co m pound o b ta in e d from E a stm a n -K o d ak C o m p an y m e lte d a t
1 7 4 -1 7 7 ° . .
.
A ttem p ts to C o n v e rt A cetam id in iu m C h lo rid e to Sodium A c e ta m id in a te
■ I t s e e m e d r e a s o n a b le th a t t h i s c o n v e r s io n c o u ld b e e ffe c te d b y r e a c t ­
in g a c e ta m id in iu m c h lo rid e w ith a so d iu m a Ik o x id e u s in g th e c o rre sp o n d in g
v a lc o h o l a s th e s o lv e n t:
H o w e v e r, th e s y s te m s em p lo y in g e th a n o l, 1 -p ro p a n o l a n d I - b u ta n o l f a ile d to
p ro d u c e s a ti s f a c to r y r e s u l t s .
The so d iu m a Ik o x id e s r e a d ily rem o v e h y d ro g e n c h lo rid e from a c e ta m i­
d in iu m c h l o r i d e . Sodium e th o x id e , h o w e v e r , r e a c te d no f a r t h e r , a s e v i­
d e n c e d b y a n e u tr a liz a tio n t e s t w ith s ta n d a rd a c i d , a n d is a p p a r e n tly n o t a
s tro n g e n o u g h b a s e to a b s tr a c t a n a m id in e p ro to n .
A lthough th e f in a l p ro d u c ts from th e so d iu m p ro p o x id e a n d sodium b u to x id e r e a c tio n s w e re n o t i s o l a t e d , r e a c tio n w ith C uC lg (2:1 m o la r ra tio ) in
9
s itu p ro d u c e d i l l - d e f in e d g re e n c o m p o u n d s „■ S u b s e q u e n t n itro g e n a n a ly s e s
p ro v e d th a t n o n e of th e s e c o m p o u n d s w a s th e d e s ir e d c o p p e r a c e ta m id in a te „
N o fu rth e r a tte m p ts w e re m ade to c h a r a c te r iz e th em „
The a n a lo g o u s r e a c tio n w ith so d iu m a m id e ,
C H 3 C (N H 2 iff, S
+ .2 N aN H 2
CH3(N H ^ N ^ +
N aC l + 2 NH3
y ie ld e d th e sam e ty p e o f p ro d u c t a s w a s o b s e r v e d to form from th e re a c tio n
b e tw e e n so d iu m am id e a n d a c e t o n i t r i l e . C o n s e q u e n tly , i t w a s c o n c lu d e d
t h a t th is r e a c tio n , a l s o , r e s u lte d in to o m uch p o ly m e riz a tio n to b e u s e f u l.
r
@1
© "
S y n th e s is o f IpH 3C(NH2) 2Jg , M C l4
(M = C u , Co)
f
©"]
©
The new compounds ICH3C(NH2)^J g » MCl4 , where M = Cu and Co,
have been prepared according to the following equation:
. 2 C H 3C (N H 2 ) f , Cl6 + M C l2 0 Zh Sq h ^ [p H 3C (N H 2)<|] 2 , M C l f .
' A nhydrous m e ta l c h lo rid e (21) a n d a c e ta m id in iu m c h lo rid e w ere m ixed
in .a m o lar ra tio of 2:1 Ifi d rie d a b s o lu te e th a n o l (2 2 ). The m e ta l c h lo rid e
w a s f i r s t d is s o lv e d in a b s o lu te e th a n o l a n d th e n a c e ta m id in iu m c h lo rid e w a s
a d d e d to th i s s o lu tio n . W h en b o th - r e a c ta n ts h a d d is s o lv e d , th e s o lu tio n s
w e re p la c e d in a d e s ic c a to r over, a n h y d ro u s e th e r .. W e ll-fo rm e d c r y s ta ls
g re w s lo w ly a s th e s o lu tio n s b e c a m e s a tu ra te d , w ith e t h e r . A fter c r y s t a l l i ­
z a tio n , th e c r y s ta ls w e re f ilte r e d a w a y from th e s o lu tio n , a n d d rie d in a v a cu u m d e s ic c a to r o v e r c o n c e n tr a te d s u lfu ric a c id . The c r y s t a l s a re o n ly
s lig h tly d e lin q u e s c e n t; h o w e v e r, to .in su re e x c lu s io n of m o is tu re , th e y w e re
s to re d in tig h tly - s to p p e r e d b o t t l e s .
T he c o p p e r c o m p le x is a n in te n s e g o ld e n y e llo w p la t e l e t c r y s t a l . It
d e c o m p o s e s a t - 1 0 8 -1 1 0 ° in the. a tm o s p h e r e .1
10
A n a ly s is : %C1, 44.0, %N, 17.2; % C u, 19.7
C a lc u la te d c o m p o s itio n o f a c e ta m id in iu m te tr a c h lo r o c u p r a te :
% C 1, 43.8; % N , 17.3; % C u , 19.7.
The c o b a lt c o m p le x p re p a re d in th is m an n er form s as-, d ark blub 'n e e d le - :
lik e c r y s ta ls w h ic h m e lt a t 2 0 7 -2 0 9 ° in th e a tm o s p h e re .
A n a ly s is : % C l , 44.5; % N , 17.3; % C o , 18.4.
C a lc u la te d p e rc e n ta g e c o m p o s itio n o f a c e ta m id in iu m te tra ch lo ro co -^
b a lta te : % C l , 44.5; % N,. 17.6; % C o, 18.5.
C h lo rid e w a s d e te rm in e d b y th e a d s o r p tio n in d ic a to r m eth o d (2 3 ), c o p p e r
w a s d e te rm in e d io d o m e tric a lly (2 4 ), n itro g e n w a s d e te rm in e d b y th e K je ld ah l
m eth o d (25), a n d c o b a lt w a s d e te rm in e d b y c o m p le x o m e tric titr a tio n w ith
e th y le n e d ia m in e te tr a a c e tic a c id (2 6 ).
All u ltr a v io le t a n d v is ib le s o lu tio n s p e c tra re p o rte d in th is th e s i s
w e re re c o rd e d a t room te m p e ra tu re by a B eckm an D K -2 s p e c tro p h o to m e te r.
T he s p e c tra o f a c e ta m id in iu m te tr a c h lo r o c u p r a te a n d a c e ta m id in iu m t e t r a c h lo r o c o b a lta te in a c e to n itr ile a re sh o w n in F ig u re s 4, 5, 6 a n d 7. A b so rp tio n
b a n d s a n d m o lar a b s o r p tiv itie s o f t h e s e s p e c tra a re l i s t e d in T a b le I .
D iffu s e r e f le c ta n c e s p e c tra a t room te m p e ra tu re o f th e c r y s ta llin e
c h lo ro c u p ra te a n d c h lo ro c o b a lta te (F ig u re s 8 a n d 9) a n d o f c o m p le x e s to be
d i s c u s s e d s u b s e q u e n tly w e re run on a B eckm an M o d el B s p e c tro p h o to m e te r.
S p e c ia l a c c e s s o r i e s u s e d for r e f le c ta n c e m e a s u re m e n ts in c lu d e a B eckm an
# 1 2 4 0 0 in te g r a tin g s p h e re r e f le c ta n c e a tta c h m e n t an d a 2000 m egohm p h o to ­
tu b e r e s i s t o r . M a g n e siu m c a rb o n a te w a s u s e d a s a r e f le c ta n c e s ta n d a rd fo r
th e c h lo ro c o b a l t a t e . B e c a u se o f th e h ig h in te n s ity o f a b s o r p tio n in th e
11
c h ltir o c u p r a te , m a g n esiu m c a r b o n a te w a s fo u n d to b e a n u n s u ita b le s t a n ­
d a rd . In th i s c a s e , th e c h lo r o c o b a lta te w a s u s e d a s th e s ta n d a r d .
The in fra re d s p e c tra o f th e te tr a c h lo r o c o m p le x e s m u lle d in n u jo l an d
flu o r o lu b e w e re ta k e n w ith a B eckm an IR -5A s p e c tro p h o to m e te r. The s p e c tra
a re id e n tic a l w ith e a c h o th e r a n d e s s e n t i a l l y id e n tic a l to th a t o f a c e ta m id inium c h l o r i d e . S p e c tra l b a n d s w ere o b s e r v e d a t 1060, 1100, 1150, 1360, 1460,
1650, 3150 a n d 32 00 w a v e n u m b e rs . A ss ig n m e n ts o f th e s e b a n d s w ill b e m ade
in th e d i s c u s s i o n .
M a g n e tic s u s c e p t i b i l i t i e s re p o rte d in th is p a p e r w e re d e te rm in e d a t
8 0 °K , 196°K a n d 298°K b y M is s K aren D ia m o n d . A G ouy b a l a n c e , c o n s is tin g
o f a M e ttle r a n a ly t ic a l b a l a n c e , a H a rv e y - W e lls M o d el L - 44V e le c tro m a g n e t
a n d a M a g n io n M o d e l.=H=HS.425 po w er s u p p ly , w a s u s e d to m ake th e m e a s u re ­
m e n ts . The e le c tro m a g n e t u s e d h a d 4" p o le c a p s w ith a v a ria b le g a p . A g a p
o f .1.5" w a s e m p lo y e d in a l l d e te r m in a tio n s . T e m p e ra tu re s o f 80°K a n d 196°K
w e re o b ta in e d from, liq u id a ir a n d d r y .ic e - a c e to n e b a t h s . The b a th s in w h ic h
th e 6 mm. G ouy tu b e w a s s u s p e n d e d w ere c o n ta in e d in a s p e c ia lly d e s ig n e d
D e w a r-ty p e f l a s k . M a g n e tic f ie ld s tr e n g th s w ere d e te rm in e d b y u s in g s
H gC o(C N S )4 (27) a s a m a g n e tic s ta n d a r d .
M a g n e tic d a ta fo r a c e ta m id in iu m te tra c h lo ro c u p r a te a re l i s t e d in
T a b le I I . P a s c a l 's c o n s ta n ts (28) h a v e b e e n u s e d for d ia m a g n e tic c o rre c ­
tio n s to th e s u s c e p t i b i l i t i e s d e te rm in e d a n d .a r e in c lu d e d in th e s u s c e p tib il­
i t i e s l i s t e d in th e t a b l e . No m e a s u re m e n ts w e re m ade o n a c e ta m id in iu m
te tr a c h lo r o c o b a lta te a t t h i s tim e .
12
W a v e le n g th (mp.)
F ig u re 4 .
U ltr a v io le t S p ectru m o f A cetam id in iu m T e tra c h lo ro c u p ra te
-
0.6
- 0.5
- 0.3
W a v e le n g th (m^)
F ig u re 5 .
V is ib le S p ectru m o f A ceta m id in iu m T e tra c h lo r o c u p r a te
13
W a v e le n g th (m^i)
F ig u re 6 .
U ltr a v io le t S pectrum o f A cetam id ln iu m T e tra c h lo ro c o b a lta te
"
0.6
W a v e le n g th (mjx)
Fig u re 7.
V is ib le S p ectru m of A c etam id in iu m T e tr a c h lo r o c o b a l ta te
'
TABLE I
S p e c tra l B ands a n d I n te n s itie s o f [CH3C(NH2) ? ]
M CI
2j 2
C o m p lex
C o n c e n tra tio n
C u p ra te
2.31 x 10-3 M
.
C o b a lta te
A b so rp tio n
W a v e le n g th (mu)
{
M o lar
A b so rp tiv ity
255
0.1
3000
307
0.1
4100
380
0.2
950
' 453
0.2
1450
■
2.30 x 10-3 M
P a th le n g th of
ra d ia tio n (cm .)
227 (sh o u ld e r)
0.1
252 .
0.1
2450
673
0.2
520
579
0.2
300
15
O p tic a l D e n s ity —A rbitrary U n it
W
8 . D iffu s e R e fle c ta n c e S p ectru m o f A cetam id in iu m T e tra c h lo ro c u p ra te
O p tic a l D e n s ity —A rb itrary U n its
S
W a v e le n g th (mg)
W a v e le n g th (mg)
F ig u re 9. D iff u s e R e f le c ta n c e Spectru m of A c etam id in iu m T e t r a c h lo r o c o b a l ta te
TABLE II
©
M a g n e tic D a ta o n [cH gC X N H g]^^ , C u C l4
T em p eratu re (0 K)
X M (°9'g , emu) x IO6
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
80
5577
1.93
196.
2462
1.92
298
1643
1.98
17
P re p a ra tio n -o f A c eta m id in iu m T ric h lo ro n ic k e la te
N ic k e l c h lo rid e d o e s n o t r e a c t w ith a c e ta m id in iu m c h lo rid e in th e
sa m e m a n n er a s d o e s C u C lg a n d C o C lg . U n d e r th e sam e c o n d itio n s th a t
C u C lg a n d C oC lg r e a c t w ith C H g C (N H g )^, Cl© to form th e te tr a c h lo r o m e ta lI a te c o m p le x e s , N iC lg r e a c t s to form th e tric h lo r o com plex,.
®
^
C H 3C (N H g)2 , C l + N iC l2
A b so lu te
E th a n o l > C H 3C (N H g)2 , N iC l3
A c eta m id in iu m c h lo rid e a n d a n h y d ro u s n ic k e l c h lo rid e w e re m ix ed in a 1:1
m o la r r a tio in a n h y d ro u s e t h a n o l .. Slow a d d itio n o f e th e r , b y th e m ethod a l ­
re a d y d e s c r ib e d , to th e r e s u ltin g y e llo w is h - g r e e n s o lu tio n p r e c ip ita te d d ark
o r a n g e , f e a th e r - lik e c r y s t a l s . The c r y s t a l s a re v e ry h y g ro s c o p ic a n d m u st
b e p r o te c te d from th e a tm o s p h e re .
A n a ly s is : % C 1, 47.4; % N , 12.5; % N i, 26.1.
©
©
C a lc u la te d .fro m C H 3C (N H 2) 2 , N iC l3 : °/oCl, 47.5; % N ,' 12.5; % N i, 26.1.
C h lo rid e a n d n itro g e n w e re d e te rm in e d b y th e a d s o r p tio n in d ic a to r a n d Kje l da h i m e th o d s r e s p e c t i v e l y . N ic k e l w a s d e te rm in e d b y c o m p le x o m e tric t i t r a ­
tio n w ith EDTA (2 9 ).
In fra re d s p e c tra o f a c e ta m id in iu m tr ic h lo r o n ic k e la te m u lle d in n u jo l
a n d flu o ro lu h e sh o w th e sa m e b a n d s a s th e ,te tra c h lo ro c u p r a te .a n d c o b a lta te
c o m p le x e s .
T he s o lu tio n sp e c tru m o f th e tr ic h lo r o n ic k e la te in a b s o lu te e th a n o l
from 360 to 1000 m(-i is sh o w n in F ig u re 10. The sp e c tru m w a s ru n w ith a
N i C J ^ c o n c e n tra tio n o f 3.49 x IO- ^ M . O ne c m . c e ll s w ere u s e d .„ Nd.a b s o r p ­
tio n w a s o b s e r v e d b e tw e e n 250 a n d 360 m ^.
X
18
The d iffu s e r e f le c ta n c e sp e c tru m o f c r y s ta ll in e a c e ta m id in iu m t r i c h lo r o n ic k e la te u s in g m a g n esiu m c a rb o n a te a s a r e f le c ta n c e s ta n d a rd is
A b so rb an c e
sh o w n in F ig u re 1 1 .
A m ax = 416
A=
770
£ = 4.8
1000
W a v e le n g th (mp.)
F ig u re 1 0.
S o lu tio n S p ectru m o f C H g C (N H g )^, N iC 1®
0.8
A b so rb an c e
-
W a v e le n g th (m|U.)
©
Q
F ig u re 1 1. D iffu s e R e fle c ta n c e S p ectru m of C H gC (N H 2) 2 / N iC lg
19
S y n th e s is o f C o p p e r (II) A c e ta m ld in a te
A fter a c e ta m id in iu m te tr a c h lo r o c u p r a te h a d b e e n s y n th e s iz e d , it p ro ­
v id e d a n ew a v e n u e fo r p o s s ib le s y n th e s is o f C u (II) A c e ta m id in a te .. R em oval
o f fo u r m o le c u le s o f h y d ro g e n c h lo rid e from C H 3 C (N H 2 )f]2 , C u C l f m ight
y ie ld th e d e s ir e d p r o d u c t, if th e re m o v a l c o u ld b e e ffe c te d w ith o u t com ­
p le te ly d e c o m p o s in g th e c h lo r o c u p r a te . W ith th i s in m in d , it w a s d e c id e d
t h a t sodium b u to x id e , a r e a s o n a b ly s tro n g b a s e ,- m ig h t b e e f f e c tiv e in r e ­
m oving th e H C l, w h ile le a v in g th e a c e ta m id in a te m o ie ty i n t a c t .
[c H 3C(N H 2) f ] 2 , C u C lf + Na®C?C4%
Cu[ c HgCt ^H) 2]
+ 4 NeCl
Sodium b u to x id e w a s p re p a re d b y re flu x in g c u t a n d d rie d sodium m e ta l
in e x c e s s re a g e n t g ra d e I-B u ta n O l fo r a b o u t a n h o u r. T h is s o lu tio n w a s th e n
a d d e d s lo w ly to a s o lu tio n o f a c e ta m id in iu m te tr a c h lo ro c u p ra te in 1 -B u ta n o l.
T he r e a c t a n t s , so d iu m b u to x id e a n d th e c h lo r o c u p r a te , w e re m ix ed in a 4:1
m o la r r a t i o . A w h ite p re c ip ita te ., la te r id e n tif ie d a s p re d o m in a n tly sodium
c h lo r id e , b e g a n to form im m e d ia te ly . S im u lta n e o u s ly , th e s o lu tio n tu rn e d
d a rk b lu e . W h en p r e c ip ita tio n s e e m e d to b e c o m p le te ,. th e s o lu tio n w as flit­
te r e d . The s o lv e n t w a s th e n re m o v e d from th e s o lu tio n .b y h ig h v a c u u m .
T h is p ro c e d u re le f t a gum w h ic h f a ile d to c r y s t a l l i z e , so th e r e a c tio n w a s
r e p e a te d to th e p o in t of v acu u m d i s t i l l a t i o n . R ath er th a n rem o v in g th e
I-B u to n a o l u n d e r v a c u u m , v a rio u s n o n -p d la r s o lv e n t s , in c lu d in g e th e r , c a r ­
b o n te tr a c h l o r id e , p -d io x a n e a n d h e x a n e , w ere a d d e d to th e f il tr a te in a n
• a tte m p t to p r e c ip ita te th e b lu e c o n s ti tu e n t. T he o n ly e f f e c t o b s e rv e d in a l l
c a s e s w a s a n a lte r a tio n in th e c o lo r o f s o lu tio n . At th is p o in t, in v e s tig a ­
tio n o f th e s y s te m w a s d is c o n tin u e d .
20
The m e ta l a m id e s a re s u f f ic ie n tly s tro n g b a s e s to rem o v e 4 m o le c u le s
I
o f h y d ro g e n c h lo rid e a n d o n e w o u ld e x p e c t to e n c o u n te r no d iff ic u lty in r e ­
m oving th e f in a l p ro d u c t from liq u id a m m o n ia . The p ro b lem is th a t th e
a m id e s a re a ls o s tro n g e n o u g h b a s e s to p ro d u c t u n d e s ir a b le s id e re a c tio n s ,
w ith th e a c e ta m id in a te . T h e s e s id e r e a c t i o n s , h o w e v e r, m ig h t b e in h ib ite d
by v a ry in g th e r e a c tio n c o n d i t i o n s .
C H 3C(NH2)^ 2C u g 5
+ 4 M NH2
7 C u (C H 3- O ^ I ) ) 2 + 4 M C l + 4 N H 3
xNH
Sodium am id e w a s p re p a re d a s d e s c r ib e d p r e v io u s ly . A s to ic h io m e tric q u a n ­
t i t y o f te tr a c h lo r o c u p ra te w a s a d d e d to th e so d iu m a m id e - liq u id am m onia
m ix tu r e . W ith in a s h o rt t i m e , th e c o n te n ts o f th e re a c tio n f la s k h a d tu rn e d
g r e e n . H o w e v e r, a f te r a b o u t a n h o u r th e s o lu tio n h a d tu rn e d b ro w n . W hen
th e am m onia h a d c o m p le te ly e v a p o r a te d , a h a rd re d d is h -b ro w n r e s i d u e , v e ry
m uch lik e th a t o b s e r v e d to form in th e N a N H 2- C H 3CN r e a c tio n , re m a in e d .
T he u s e o f p o ta s s iu m a m id e w a s m uch m ore f r u itf u l. A g a in , th e KNH2
w a s p re p a re d by th e m eth o d o f G re e n le e a n d H eh n e w ith th e a d $ e d p re c a u ­
tio n o f d ry in g th e a m m o n ia 1. A fter th e KNH2 h a d b e e n p re p a re d in th e d rie d
a m m o n ia , th e c u p ra te c o m p le x w a s a d d e d . The s to ic h io m e tric q u a n tity w a s
a d d e d in to to to th e w e l l - s t i r r e d m ix tu re to a v o id a s m any u n d e s ir a b le s id e
r e a c tio n s a s p o s s i b l e . T he d a rk g re e n c o lo r o f th e am m onia s o lu tio n p e r­
s i s t e d in th is c a s e u n til e v a p o ra tio n w a s c o m p le te . A g a in , m uch r e d d is h brow n re s id u e re m a in e d ; h o w e v e r, th is w a s in te r s p e r s e d b y a d ark g re e n .
r e s i d u e . A b so lu te e th a n o l w a s th e n a d d e d to th is m ixed r e s i d u e . W ith in
I.
The d ry in g o f th e am m onia s e e m s to b e v e ry c r i t i c a l . In a l l c a s e s in
w h ic h t h i s w a s n e g le c te d , r e s u lts s im ila r to th o s e o f th e .s o d iu m r e a c ­
tio n w e re o b t a i n e d .
21
th r e e - f o u r h o u r s , th e e th a n o l h a d a s s u m e d a d ark b lu e c o lo r . T h is 'm ix tu re
w a s p e r io d ic a lly s h a k e n o v e r a p e rio d o f e ig h t to tw e lv e h o u rs to e x tr a c t a s
m uch o f th e g re e n r e s id u e a s p o s s i b l e . The s o lu tio n w a s th e n f ilte r e d a n d
th e e th a n o l w a s a llo w e d to e v a p o ra te in th e a tm o s p h e re . W h en n e a rly a l l
th e e th a n o l h a d e v a p o r a te d , d a rk b lu e c r y s t a l s h a d fo rm e d . T h e s e w ere f i l ­
te r e d a w a y from th e e th a n o l a n d d rie d o v e r c o n c e n tr a te d s u lfu ric a c id in
v a c u o for tw e lv e h o u r s .
T he c r y s t a l s w e re re w a s h e d w ith d ry e th a n o l, re d rie d in v a c u o , an d
h e a te d in a n o v e n a t 8 0 - 8 5 ° for o n e h o u r. T h is p ro c e d u re b ro u g h t th e num ­
b e r o f m o le c u le s o f s o lv a tio n q u ite c lo s e to o n e . Y ie ld s w e re from 2 0-3.0% .
F in a l a n a l y s i s : % C u , 37.8; % N , 24.5.
C a lc u la te d fo r1C u ^ lH g C (N H ) 2 2 • I E tO H : % C u , 28.4; .%N„ 25.0.
T he b lu e c r y s ta ls a re in s o lu b le in m o st o f th e com m on c ry o s c o p ic a n d
e b u llio s c o p ic s o lv e n ts .. The o n ly s o lv e n ts fo u n d in w h ic h th e y w ere s o lu b le
w e re e th a n o l a n d d im e th y l s u lf o x id e . H e a tin g th e e th a n o l - C u (II) A c e ta m id in a te s o lu tio n to th e b o ilin g p o in t o f e th a n o l d e c o m p o se d th e a m id in a te . No
c ry o s c o p ic o r e b u llio s c o p ic d a ta o n DMSO a re p r e s e n tly a v a i l a b l e . C o n s e ­
q u e n tly , no m o le c u la r w e ig h t d e te rm in a tio n .w a s m ade o n C u(II) A c e ta m id in a te .
Solutiop. s p e c tra o f C u(II) IjC H gC (N H )^ g ° I EtOH in DM SO a re show n
in F ig u re s 12 a n d 13. A b so rp tio n b a n d s a n d m o lar a b s o r p tiv itie s fo r th e
c o m p le x a re re p o rte d in T a b le I I I . The d iff u s e r e f le c ta n c e s p e c tru m o f th e
c r y s ta ll in e a c e ta m id in a te u s in g m a g n esiu m c a rb o n a te a s a r e f le c ta n c e s t a n ­
d a rd i s sh o w n in F ig u re 14. An in fra re d sp e c tru m o f C u(II) A c e ta m id in a te in a
KBr m ic ro p e lle t is sh o w n in F ig u re 15. M a g n e tic d a ta fo r t h i s c o m p le x a re
22
l i s t e d in T a b le IV. P a s c a l 's c o n s ta n ts h a v e b e e n in c lu d e d in th e s u s c e p t i ­
b i l i t i e s sh o w n .
S y n th e s is o f C o p p er (II) B e n z a m id in a te
P o ta s s iu m b e n z a ^ n id in a te is m uch m ore r e a d ily p re p a re d th a n p o ta s ­
siu m a c e ta m id in a te . The s a l t w a s m ade by re a c tin g p o ta s s iu m am id e w ith
d o u b le - d is tille d b e n z o n itrile in d rie d liq u id a m m o n ia .
KNH 2 + <p-CN
NH3 ^1^>
Y ie ld s o f 50-70% w e re o b ta in e d from t h i s r e a c tio n .
The potassium benzamidinate prepared by this procedure was then re­
acted with anhydrous CuClg in a 2:1 molar ratio.
2 <p-C(NH )f ,K* + CuCl2
2~Pr0Pan0l>[cu ^ - C ( N H ) J 2 + 2 KCl
CuCl2 w a s f ir s t d is s o lv e d in is o p ro p y l a lc o h o l a n d to th is s o lu tio n th e a p ­
p ropriate q u a n tity o f p o ta s s iu m b e n z a m id in a te w a s a d d e d . P o ta s s iu m b e n z ­
a m id in a te is e s s e n t i a l l y in s o lu b le in is o p ro p y l a lc o h o l. W hen it w a s a d d e d
to th e C u C l2 s o lu tio n , th e r e s u lta n t m ix tu re tu rn e d d ark g r e e n . A fter a h a lf h o u r o f s t i r r i n g , th e m ix tu re h a d tu rn e d c a n a ry y e llo w . T h is y e llo w m a te ria l
w a s f ilte r e d a w a y from th e is o p ro p y l a lc o h o l a n d p la c e d in e th a n o l. The
e th a n o l g ra d u a lly a s s u m e d a b lu is h - p u r p le c o lo r . A fter te n h o u rs of s tirrin g
th is m ix tu re , th e b lu e e th a n o l s o lu tio n w a s f ilte r e d a w a y a n d p la c e d in an
e v a p o ra tin g d is h e x p o s e d to th e a tm o s p h e re .
P u rp le c r y s t a l s form ed a s th e e th a n o l e v a p o r a te d . T h e s e w ere w a s h e d
s e v e r a l tim e s w ith c o ld a b s o lu te e th a n o l, d rie d o v e r c o n c e n tra te d s u lfu ric
a c id in v a c u o , a n d f in a lly d rie d in a n o v e n a t 80°C for o n e h o u r. Y ield s of
15-20% w e re o b ta in e d .
23
A n a ly s is : % C u , 18.5; % N, 1 6 .3 .
Calculated for C u jip C tN H ^ ° I EtOH: %Cu, 18.4; %N, 16.1.
The b e n z a m id in a te c o m p le x d e c o m p o s e s a t 1 7 0 -1 7 5 ° C . H e a tin g a b o v e
120° for p ro lo n g e d p e rio d s re m o v e s e th a n o l o f s o lv a tio n .
C u (II) b e n z a m id in a te is in s o lu b le in th e sam e s o lv e n ts in w h ic h c o p ­
p e r (II) a c e ta m id in a te is in s o lu b le .
S o lu tio n s p e c tra of c o p p e r (II) b e n z a m id in a te in DMSO a re show n in
F ig u re s 16 an d 17. A b so rp tio n b a n d s an d m o lar a b s o r p tiv itie s a re lis t e d in
T a b le II I. The d iffu s e r e f le c ta n c e sp e c tru m u s in g m a g n esiu m c a rb o n a te a s a
s ta n d a rd is sh o w n in F ig u re 18.
M a g n e tic d a ta for th is c o m p le x a re re c o rd e d in T ab le IV. P a s c a l 's
d ia m a g n e tic c o r r e c tio n s a re in c lu d e d in th e s u s c e p t i b i l i t i e s .
W a v e le n g th (m^i)
F ig u re 12
U l tr a v io le t S p ectru m of Cu [CH3C (N H )2] , • EtOH
A b so rb an c e
24
W a v e le n g th (m|i)
O p tic a l D e n s ity —A rb itrary U n its
F ig u re 13. V is ib le S p ectru m o f Cu [C H 3C (N H )2J 2 • EtOH
W a v e le n g th (mp.)
F ig u re 14. R e f le c ta n c e Spectru m of C u j c H 3C(NH)2J ■ • EtOH
P e rc e n t T ra n s m itta n c e
25
4500
W av en u m b er in K a y se rs
A b so rb a n c e
F ig u re 15. In fra re d S pectru m o f C ujjcH gC fN H jgjg • EtOH
W a v e le n g th (mfi)
F ig u re 16. U l tr a v io le t S p ectru m of Cu[cpC(NH)2]2 * EtOH
A b so rb an c e
26
W a v e le n g th (m )
O p tic a l D e n s ity —A rb itrary U n its
F ig u re 17. V is ib le S p ectru m o f CuljtpCXNHjgjg ' EtOH
W a v e le n g th (m|4)
F ig u re 18. R e f le c ta n c e S p e c tru m of Cu[(pC(NH)2]- • EtOH
TABLE III
S p e c tr a l Bands a n d S p e c tr a l I n t e n s i t i e s of C o p p e r (II) A m id in a te s
C om pound
C o n c e n tr a tio n
in DMSO .
A c e ta m id in a te
1.8 x 10" 3 M
B e n z a m id in a te
9.8 x IO" 4 M
A b so rp tio n
W a v e le n g th (mjui)
P a th le n g th of
R a d ia tio n (c m .)
M o lar
A b so rp tiv ity
302
0.1
2610
570
1.0
93
300 (sh o u ld er)
0.1
578
1.0
133 •
TABLE IV
M a g n e tic D a ta o n C o p p e r (II) A m id in a te s
C om pound
A c e ta m id in a te
B e n z a m id in a te
T e m p e ra tu re (0 K)
% M (e g s , emu) x IO6
M a g n e tic S u s c e p t i b i l i t y
80
5546
1.89.
196
2291 '
1.90
297
1470
1.89
80
5883
1.94
196
3078 .
2.19
297
2140
2.26
(b . m .)
M om ent
k
DISCUSSION
A c eta m id in iu m T e tr a c h lo r o c u p r a te
The c h lo r o c u p r a te e x h i b i t s a f a ir ly s tro n g ( £ = 1450 in s o lu tio n s p e c trum) a b s o r p tio n b a n d a t a b o u t 450 m|X (22,200 c m .
a n d a c e t o n i t r i l e spectra),. All o f th e
_
in b o th i t s c r y s t a l l i n e
s h o w a c h a rg e
t r a n s f e r b a n d in t h i s r e g io n . G ^ C u C l ^ k n o w n to h a v e a d is to rte d , t e t r a h e d r a l s tr u c tu r e (3 0 ), s h o w s a c h a r g e t r a n s f e r b a n d a t 24,800 c m :
(31) a t
7 7°K . ^Pt(NHg)4] [CUCI4J , a s q u a r e p la n a r s tr u c tu r e (32), e x h i b i t s a c h a rg e
t r a n s f e r b a n d a t 24,900 c m .
(33). C s C u C lg h a s . a d i s t o r t e d o c t a h e d r a l
l a y e r s tr u c tu r e in w h ic h e a c h c o p p e r io n i s s u rro u n d e d b y fo u r n e a r e s t
c h l o r i d e s . T h is c o m p le x h a s a c h a r g e t r a n s f e r b a n d a t 24,600 c m .
Sm ith a n d G rif fith s (34) re p o rt a b a n d a t 22,200 c m .
(33).
for C u C lg i n a m elt of
t r i b u t y l - 2, 4 - d ic h lo r o b e n z y lp h o s p h o n iu m c h l o r i d e . They c o n s i d e r t h i s b a n d
a n d th e d - d b a n d a t 8000 c m . I a s c r ite r ia for t e t r a h e d r a l C u C i4 . The f a c t
t h a t th e square, p la n a r s t r u c t u r e s e x h ib it s im ila r b a n d s , h o w e v e r , r e n d e rs a n
u n e q u iv o c a l s t r u c t u r a l c o n c l u s i o n , o n t h i s b a s i s a l o n e , d if f ic u l t if no t im­
p o ssib le .
The m a g n e tic m om ent o f th e c u p r a te c o m p le x o v e r th e te m p e ra tu re
ra n g e 8 0 -2 9 8 ° K a p p e a r s to be e s s e n t i a l l y te m p e ra tu re i n d e p e n d e n t ,, c h a r a c ' t e r i s t i c of m a g n e t ic a lly d ilu te c o m p l e x e s . A lthough o n ly three, p o in ts w ere
o b t a i n e d , a p lo t of s u s c e p t i b i l i t y v e r s u s te m p e ra tu re s u g g e s t s t h a t . t h e co m ­
plex. f o llo w s t h e C u r i e - W e i s s Law in t h e 80-298PK te m p e r a tu r e r a n g e . A lo w
W e i s s c o n s t a n t o f a b o u t -1 2 ° i s o b ta in e d by p lo ttin g (X m ^_1 v e r s u s TC u C lg / w h ic h i s a n tif e r r o m a g n e tic w ith a c r i t i c a l te m p e ra tu re of 7 0°K (35),
h a s a s tr u c tu r e i n w h ic h C u i s b r id g e d b y tw o C l ' s (36). L iC u C lg d ih y d ra te
a n d KCuClg a l s o h a v e c h lo r id e b r id g e d s tr u c tu r e s , and show a h tif e r r o m a g n e tic
30
b e h a v io r (3 7 ). All t h e s e f a c t o r s t e n d to i n d i c a t e t h a t a c e ta m ld in iu m t e t r a c h lo r o c u p r a te i s n o t a n tif e r r o m a g n e tic a n d d o e s n o t c o n ta i n c o p p e r b rid g e d
b y tw o c h l o r i d e s .
F ig g is a n d H a rris (38) l i s t a .m o m e n t o f 2.00 for C s g C u C l^ a n d s u g g e s t
t h a t th e m a g n e tic m o m en ts o f t e t r a h e d r a l c o p p e r c o m p le x e s m ay b e h ig h e r
t h a n th e m o m en ts fo r s q u a r e p la n a r c o m p l e x e s . [Pt(N H g)^.j~CuCl4j h a s a
m om ent of 1.77 (3 3 ). A c eta m ld in iu m t e t r a c h l o r o c u p r a t e h a s a room te m p e r a ­
tu r e m om ent o f 1.98.
O n th e b a s i s o f th e e v id e n c e a v a i l a b l e a t th e p r e s e n t tim e ,
[ p H 3C (N H 2 ) ^ 2 / -C u C l^ p ro b a b ly d o e s n o t h a v e a n i s o l a t e d s q u a r e p la n a r
s t r u c t u r e . The p r e s e n t e v id e n c e s e e m s to i n d i c a t e a t e t r a h e d r a l s tru c tu re „
AU o f th e i n f r a r e d a b s o r p tio n b a n d s l i s t e d o n p a g e 12 m ay b e a s s i g n e d
to th e a c e ta m ld in iu m c a t i o n . The f a c t t h a t th e in fra re d s p e c t r a of a c e t a m i d in iu m c h lo r id e a n d a c e ta m id in iu m te tr a c h l o r o c u p r a t e a re i d e n t i c a l s u g g e s t s
t h a t th e c u p r a te c o m p le x c o n t a i n s t h e ’a c e ta m id in iu m c a t i o n a n d n o t a c o ­
o r d i n a t e d a c e ta m id in iu m s p e c i e s .
A c eta m id in iu m T e tr a c h lo r o c o b a l ta te
©
F e r g u s o n (39) h a s re p o r te d th e c r y s t a l f i e l d s p e c tru m of C 0 C I4 in s e v ­
e r a l c r y s t a l l i n e e n v ir o n m e n ts . He p o in ts o u t t h a t th e v i s i b l e a b s o r p tio n
©
b a n d s for th e d i s t o r t e d t e t r a h e d r a l C o C l 4 f a l l in to th re e m a in r e g i o n s , 14000
to n e a r ly 17000 c m ." 1 , 17,200 to a l i t t l e more t h a n 20,000 c m a n d
22,000
,
to a l i t t l e a b o v e 24,000 c m .- 1 . The d if f u s e r e f l e c t a n c e s p e c tru m o f a c e t a m i ­
d in iu m t e t r a c h l o r o c o b a Ttate h a s b a n d s a t 23 ,8 0 0 , 22,200, 19,000 .a n d ab o u t.
14,500 c m .- l . All o f t h e o b s e r v e d a b s o r p tio n b a n d s c a n b e t h e o r e t i c a l l y
31
a s s i g n e d to t e t r a h e d r a l CoCl^f. W ith o u t a d d i t i o n a l e v i d e n c e , th e p r e s e n c e
0
o f t e t r a h e d r a l C 0 C I4 in a c e ta m id in iu m t e t r a c h l o r o c o b a l t a t e i s s tro n g ly
fav o red .
A g a in , th e in fr a r e d s p e c tru m i n d i c a t e s t h a t th e a c e t a m idinium c a ti o n
i s p r e s e n t in th e c h l o r o c o b a l t a t e c o m p l e x .
A c eta m id ln iu m T r ic h l o r o n ic k e la te
©
Very l i t t l e s e e m s to b e k now n a b o u t th e N iC lg s p e c i e s . It i s i n t e r e s t ­
in g t h a t th e a c e ta m id in iu m a n a lo g y to c e s iu m m ay be e x te n d e d to t h i s c a s e
a l s o . The c r y s t a l s tr u c tu r e o f C s N iC lg h a s b e e n a llu d e d to b y W e ll s (40).
The s tr u c tu r e i s o n e in w h ic h o c t a h e d r a l N iC lg g ro u p s s h a r in g a p a ir of o p ­
p o s i t e f a c e s a r e s t a c k e d in c o l u m n s .
A c e ta m id in iu m t r i c h l o r o n i c k e l a t e in e t h a n o l s h o w s a b s o r p t i o n b a n d s a t
24,100 a n d 13,000 c m .- -*- w ith v e ry lo w m olar a b s o r p t i v i t i e s of 12.3 a n d 4.8 r e ­
s p e c t i v e l y . A c h a r a c t e r i s t i c fe a tu r e o f o c t a h e d r a l Ni (II) c o m p le x e s i s th a t
t h e y p o s s e s s v e r y lo w m o la r a b s o r p t i v i t i e s (41). T y p ic a l o c t a h e d r a l Ni (II)
c o m p le x e s s u c h a s [N i(H g G )^ ^ a n d [N i( e th y le n e d ia m in e ) 3J
a b s o r p t i o n b a n d s b e tw e e n 11,000 a n d 15,000 c m .
a lso have
-I '
-I
a n d a ro u n d 25,000 cm . .
If t h e t f i c h l o r o n i c k e l a t e i s p r e s e n t in s o lu tio n a s N iC l^ a n d n o t . a s a com ­
p le x m ix tu re o f [N iC ln L ^ rJ n ^ , th e -so lu tio n s p e c tru m s tr o n g ly s u g g e s t s
. t h a t th e c o m p le x is o c t a h e d r a l .
C o p p e r (II) A c e ta m id in a te a n d C o p p e r (II) B e n z a m id in a te
The e le m e n ta l a n a l y s e s o n b o th t h e s e c o m p le x e s i n d i c a t e a s in g le
m o le c u le o f s o l v a t i o n . T h is i s the. c o r r e c t s to ic h io m e tr y for a d i m e r i c s y n s y n b i d e n t a t e s t r u c t u r e . U n f o r t u n a te ly , th e c o m p le x e s a re so in s o lu b le in
m o s t com m on s o lv e n ts , t h a t th e ,m o le c u la r w eights, c o u ld n o t b e d e te r m in e d .
32
The c r y s t a l a n d s o l u t i o n s p e c tr a o f t h e tw o c o m p le x e s i n d i c a t e th a t
t h e y h a v e v e ry s im ila r s t r u c t u r e s . B ands a ro u n d 580 mpi a re n o t o b s e r v e d in
th e s p e c tr a o f t h e Cu (II) c a rb o x y la te .s ; h o w e v e r,. 1 ,3 - D ip h e n y l t r i a z e n i d o c o p p e r (I I), p re s u m e d to h a v e a s y n - s y n b i d e n t a t e s t r u c t u r e , d o e s a b s o r b
n e a r 600 mj-c (13). O n th e o th e r h a n d , G o u ld a n d J a m e s o n (42) re p o rt a b s o r p ­
t i o n b a n d s a t a b o u t 580 m ptfor th r e e oL-hydroxyam idine c o m p le x e s w ith c o p ­
p e r (I I). T h ey p ro p o s e for t h e s e c o m p le x e s a s tr u c tu r e in w h ic h th e oCh y d ro x y a m id in e lig a n d a c t s a s a c h e l a t e g r o u p , c o o r d in a tin g w ith th e c o p p e r
th ro u g h o n e n itr o g e n a n d th p h y d ro x y o x y g e n . Two of t h e i r re p o r te d com.p l e x e s a r e d ih y d r a te d , th e o th e r b e in g a n h y d r o u s .
-
*
If o n e p lo ts th e m a g n e tic s u s c e p t i b i l i t i e s v e r s u s te m p e r a tu r e for e a c h
o f th e a m id in a te c o m p l e x e s , r e a s o n a b l e p a r a b o la s m ay b e d ra w n th ro u g h th e
t h r e e p o in ts in e a c h c a s e . The s u s c e p t i b i l i t i e s a p p e a r to 'c o n f o rm to th e
C u r i e - W e i s s Law in t h e 8 0 -2 9 8 ° K te m p e r a tu r e r a n g e . S u s c e p t i b i l i t i e s a t a
fe w in te r m e d ia te te m p e ra tu re s ' w o u ld co n firm t h i s . W e i s s c o n s t a n t s of a b o u t
+ 1° a n d - 20° a re o b ta in e d for t h e a c e t a m i d i n a t e a n d b e n z a m id in a te r e s p e c t ­
i v e l y , im p ly in g t h a t th e c o m p le x e s a re n o t a n tif e r r o m a g n e tic . Q u ite n o rm a l,
te m p e r a t u r e - i n d e p e n d e n t m a g n e tic m o m en ts w e re d e te r m in e d fo r b o th com ­
p l e x e s , s u g g e s t i n g t h a t th e c o m p le x e s a r e m a g n e t ic a lly d i l u t e .
Q n th e b a s i s o f th e e x p e r im e n t a l d a ta d e te rm in e d a t t h e tim e of t h i s
w r i t i n g , l i t t l e more c a n b e s a i d a b o u t t h e s e c o m p l e x e s . I n i t i a l s t u d i e s s e e m
to h in t t h a t c o p p e r (II) a c e t a m i d i n a t e a n d c o p p e r (II) b e n z a m id in a te m ay no t
b e d im e r ic . H o w e v e r , u n t i l a m o le c u la r w e ig h t (or c r y s ta ll o g r a p h i c ) d e t e r ­
m in a tio n i s m a d e , o n e c a n n o t b e c e r t a i n o f t h i s .
SUMMARY
C o p p e r (II) a c e t a m i d i n a t e i s m uch more d if f ic u l t to s y n t h e s i z e .th a n
i n i t i a l l y a n t i c i p a t e d . The m o s t f e a s i b l e a n d d ir e c t a p p r o a c h .
C H 3CN + KNH3 .
GH3C (N H )^z f
C u C l2 + 2 CH3C (N H )f, f
C u [c H 3C (NH)2J 2 + 2 K C lz
f a i l e d to p ro d u c e th e d e s i r e d p r o d u c t . W h ile i n v e s t i g a t i n g o th e r p o s s i b l e
a p p r o a c h e s , th r e e n e w c o m p l e x e s , a c e ta m id in iu m te tr a c h l o r o c u p r a t e , a c e t a m id in iu m t e t r a c h l o r o c o b a l t a t e a n d a c e ta m id in iu m t r i c h l o r o n i c k e l a t e w ere
p r e p a r e d . O ne o f t h e s e c o m p l e x e s , t h e c u p r a t e , w a s u s e d .as. a n in te rm e d i­
a t e in th e s u c c e s s f u l s y n t h e s i s of c o p p e r (II) a c e t a m i d i n a t e . The g e n e r a l
: s y n t h e s i s o f th e l a t t e r i s a s fo llo w s :
/# 2
ZP C 2H 3 C 2H 5OH
C H 3CN + C 2H5 OH + H C l — > C H 3C
NH3
C H 3C\ v®
N H z Cl
NHr
© ©
2 CH3C (N H 2) f , C ® + C uC l2
^2^5° ^
S
^C H 3C (NH2)© ^ ; CuC1®
[CH3C (N H 2)^ j2 , C u C lf + 4 KNH2 N - 23—-> -Cu[cH3C (NH)2J2 + 4KC1 + 4NH3
C o p p e r (II) b e n z a m id in a te h a s b e e n p r e p a r e d b y th e d ir e c t m e th o d ,
p - C N + KNH2
N H 3 ^ -> y - C ( N H ) f , K
2 ^ - C ( N H ) f z K + C u C l2
-3-H — - -> C u [c (NH)2Jj2 + 2 KCl
U l t r a v i o l e t a n d v i s i b l e s o lu tio n sp.ectra a n d d iff u s e r e f l e c t a n c e : 's p e c ­
tr a h a v e b e e n r e p o r te d for a l l fiv e o f t h e s e . n e w c o m p l e x e s . M a g n e tic s u s ­
c e p t i b i l i t i e s a t 8 0°, 196° a n d 2 9 S0K h a v e b e e n d e te r m in e d a n d . re p o r te d for
a c e ta m id in iu m t e t r a c h l o r o c u p r a t e , c o p p e r (II) a c e t a m i d i n a t e a n d c o p p e r (II)
b e n z a m id in a te .
34
LITERATURE CITED
1. J. N . v a n N ie k irk a n d F, R. L. S c h o e n i n g Acta C r y s t .,
6, 609, (1953).
2.
J. N . v a n
N ie k irk a n d F. R. L„ S c h o e n i n g , Ib id 22 7.
3.
J. N . v a n
N i e k i r k , F. R . L . S c h o e n i n g , a n d J„ H . T a l b o t ,
4 . J. N . v a n N i e k i r k , F. R. L . S c h o e n i n g , a n d J. F. de W e t , Ib id
Ib id 720.
501 „
5 . M , A. P o r a i- K o s h its a n d A. S. A n ts y s h k in a , D o k l . A k a d . N auk . SSSR,
146, 1 1 0 2 , (1 9 6 2 ).
6 . B. N . F ig g is a n d R. L. M a r tin , T. C h e m . S o c . , 3837 (1 9 5 6 ).
I
7 . L G . R o s s , T r a n s . F a r a d a y S o c . , 5 5 , 1057 (1959).
8 . E . A . IB o h d re a u x , I n o r g . C h e m . , 3 , 5 0 6 , (1 9 6 4 ).
9 . L. 5 . F o r s te r a n d C . T. B a llh a u s e n , Acta Chem.. S c a n d ., 16, 1385 (1962).
1 0 . R. K iriv a m a , H . I b a m o t o , a n d K. M a t s u o , Acta C r y s t ., 7, 4 8 2 ,( 1 9 5 4 ) .
1 1 . G . A. B a rc la y a n d R. L. K e n n a rd , T. Cherru S o c ., 3289 (1 9 6 1 ).
1 2 . R. L. M a r tin a n d H . W a te r m a n , I. C h e m . S o c ., 1359 (1 9 5 9 ).
1 3 . C . M . H a r r i s , B. F. H o s k i n s , a n d R . L . M a r tin , I. C h e m . S o c ., 3728
(1959).
1 4 . K .W . G r e e n l e e a n d A. L. H e n n e , In o r g a n ic S y n t h e s e s , Volume I I , W. C.
F e r n e l i u s , e d i t o r - i n - c h i e f , M c G r a w - H ill C om pany, N ew Y ork, 1946,
p . 128.
1 5 . E . F. C o r n e l l , T. Am. C h e m . Soc ., 5 0 , 3311 (1928).
1 6 . A. W. D o x , O rg a n ic S y n t h e s e s , C o l l . Volume I , H e n ry G ilm a n a n d A. W.
B l a t t , e d i t o r s - i n - c h i e f , John W ile y a n d Sons , I n c . , N ew Y o rk , N . Y.,
1 9 4 1 , p . 5.
35
1 7 . A. P in n e r , B e r., 16, 1643 (1883); 17, 171 (1884)
1 8 . H a n d b o o k of C h e m is tr y a n d P h y s i c s , C h a r l e s D. H o d g m a n , e d i t o r - i n c h i e f , C h e m ic a l R ubber P u b lis h in g C o . , 1 9 5 8 - 1 9 5 9 , p . 7 6 6 .
1 9 . H a n d b o o k of C h e m i s t r y , N o rb e rt A. L a n g e , e d i t o r - i n - c h i e f , H an d b o o k
P u b l i s h e r s , I h c . , Sandusky-, O h io , 1956, p . 3 8 4 .
2 0 . G e o rg e S . Ham m ond a n d R obert C . N e u m a n , Tr., I. P h y s . C h e m ., 67,
1655 (1 9 6 3 ).
2 1 . Alfred R. P r a y , In o r g a n ic S y n t h e s e s , Volume V, T h e ra ld M o e l l e r , e d ito r
i n - c h i e f , M c G r a w - H ill Book C o m p a n y , N ew Y o rk > 1957, p . 153.
2 2 . H . Lund a n d T. B ie rru m , B e r., 6 4 , 211 (1 9 3 1 ).
2 3 . L. H a m ilto n a n d S. S im p s o n , Q u a n tita tiv e C h e m ic a l A n a l y s i s , E le v e n th
E d itio n , The M a c M illa n C o m p a n y , N ew Y o rk , 1958, p . 3 0 0 .
2 4 . L. H a m ilto n a n d S. S im p s o n , I b id , p . 270.
2 5 . J. KieIdahl,, Z . A n a l. C h e m ., 2 2 , 366 (1 8 8 3 ).
2 6 . F. J. W e l c h e r , The A n a ly tic a l U s e s of E t h y l e n e d i a m i n e t e t r a a c e t i c A c id ,
D. Van N o s tr a h d C o m p a n y , Inc ., P r i n c e t o n , N . J., 1 9 5 8 , p . 2 3 0 .
27'. B. N . F ig g is a n d R. S . N y h o lm , T. C h e m . S o c ., 4190 (1 9 5 8 ).
2 8 . P. W. S e l w o o d , M a g n e t o c h e m i s t r y , S e c o n d E d itio n , I n t e r s c i e n c e Pub­
l i s h e r s , I n c . , N ew Y o rk , 1 9 5 6 , p . 9 2 .
2 9 . F. T. W e l c h e r , The A n a ly tic a l U s e s of E t h y l e n e d i a m i n e t e t r a a c e t i c A c id ,
D . Van N o s tr a n d C o m p a n y , I n c . , P r in c e to n , N . J . , 1958, p , 236.
30. L. H e lm h o lz a n d -R. F. K ru h , T. Am. Chem.. S o c ., 7 4 , 1176 (1 9 5 2 ).
3 1 . T. F e r g u s o n , T. C h e m . P h y s ., 4 0 , 3406 (1 9 6 4 ),
36
3 2 . M . B ukorska a n d M . A . P o r a l- K o s h its >!..K ris ta llo q fa H y a ,, 5, 127 (1960)
3 3 . W. E. H a tf ie ld a n d T. S. P i p e r , I n o r g a n ic C h e m i s t r y , 3 , 841 (1964).
3 4 . G . P. Sm ith a n d T. R. G rif fith s , T. Am. C h e m . S o c ., 8 5 , 4051 (1963).
3 5 . C . G . B arra clo u q h a n d C . F. N q , T r a n s . F a r a d a y S o c ., 6 0 , 837 (1964).
3 6 . A, F. W e l l s , S tr u c tu r a l I n o r g a n ic C h e m i s t r y , 3rd e d i t i o n , O xford U niliv e rsity P r e s s , London, 1962, p . 875.
3 7 . R . D . W i l l e t , C . D w ig g in s , R . F. K ru h , a n d R. E. R undle , I. C h e m .
P h y s ., 3 8 , 2429 (1 9 6 3 ).
3 8 . B. N . F ig g is a n d C . M . H a rris , T. Chem-. S o c ., 855 (1 9 5 9 ).
3 9 . I. F e r g u s o n , T. C h e m . P h y s ., 3 9 , 1 16 (1 9 6 3 ).
4 0 . A. F. W e l l s , S tr u c tu r a l In o r g a n ic C h e m i s t r y , p . 377 .
4 1 . F. C o tto n a n d G . W i l k i n s o n , A d v a n ce d I n o r g a n ic C h e m i s t r y , I n t e r s c i e n c e P u b l i s h e r s , N e w Y ork, 1962, p . 7 3 5 .
4 2 . R. O. G o u ld a n d R. F. T a m e s o n , T. C h e m . S o c ., 15 (1 9 6 3 ).
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