IH, 13C AND 199Hg NMR STUDIES OF THE --NHCSCONTAINING

8/20/2019 IH, 13C AND 199Hg NMR STUDIES OF THE --NHCSCONTAINING

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Pergamon

0277-5387 95)00505-6

ollhedron

V o l 1 5 . N o 1 4 . p p . 2 : ~ 97 2 4 0 1 , 1 9 9 6

C o p y r i g h t i 1 9 96 E l s e v i e r S c i e n c e L t d

P r i n t e d i n G r e a t B r i t a i n . A l l r i g h t s r e s e r v e d

1 12 77 5 3 8 7 9 6 1 5 0 0 + 0 0 0

IH

3C

A N D 199Hg N M R S T U D I E S O F T H E - - N H C S -

C O N T A I N I N G L I G A N D S W I T H M E R C U R I C H A L I D E S

A N V A R H U S E I N A . I SA B * an d H E R M A N P . P E R Z A N O W S K i

D e p a r t m e n t o f C h e m i s t ry , K i n g F a h d U n i v e r s i t y o f P e t r o l e u m a n d M i n e r a ls ,

D h a h r a n 3 1 2 6 1 , S a u d i A r a b i a

Received 12 July 1995, accepted 5 October 1995)

A b s t r a e t - - T h e r e a c t io n o f m e r c u r y ( I I ) h a li d e s w it h i m i d a z o l id i n e - 2 -t h i o n e , 1 , 3 -d i az i n an e -

2 - t h i o n e a n d 1 , 3 - d i a z e p i n e - 2 - th i o n e y i e l d ed c o m p l e x e s o f s to i c h i o m e t r y H g L 2 C I 2 a n d

H g L 2 B r2 . T h e C ( 2 ) r e s o n a n c e o f a l l t h i o n e l i g a n d s s h i f t e d m o r e f o r H g B r 2 c o m p l e x e s

c o m p a r e d w i th H gC 12 . T h e 1 99 Hg N M R c h e m i c a l s h i ft r a n g e is w i t h i n - 8 0 5 t o - 1 00 8 p p m

f o r H g L 2C I2 c o m p l e x e s a n d - 1 1 2 4 t o - 1 3 9 4 p p m f o r al l H g L 2B r 2 c o m p l e x e s . A ls o ~ C

a n d 1 99 H g N M R c h e m i c a l s h if t s a r e c o m p a r e d f o r fi v e- , s ix - a n d s e v e n - m e m b e r e d l ig a n d s

a f t e r c o m p l e x i n g w i t h m e r c u r i c h a l id e s . C o p y r i g h t : ( 1 99 6 E l se v i e r S c i en c e L t d .

T h e c o o r d i n a t i o n c h e m i s t r y o f t h e t h i o a m i d o g r o u p

- - N H C S i n h e t e ro c y c l ic p e n t a - , h e x a - a n d h e p t a -

a t o m i c r in g s , s u c h a s i m i d a z o l i d i n e - 2 - t h i o n e ( I m t ) ,

1 , 3 - d i a z i n a n e - 2 - t h i o n e ( D i a z ) a n d 1 , 3 - d i a z e p i n e - 2 -

t h i o n e ( D i a p ) h a s b e e n t h e s u b j e c t o f s e v e ra l r e c e n t

s t ud i es . ~ 9

I n o u r p r e v i o u s s t u d i e s w e r e p o r t e d t h e ~ H , 1 3 C

a n d ~ 99H g N M R s tu d ie s o f th e c o m p l e x a t i o n o f

H g C I 2 b y I m t a n d i ts d e r i v a t iv e s . 9 I t w a s f o u n d t h a t

~ 99 Hg c h e m i c a l s h i f t s a r e s e n s i t i v e t o t h e d i f f e r e n t

s u b s t i t u e n t s o n t h e N H , N H i m i d a z o l e r in g . I n th i s

p a p e r , w e e x t e n d o u r s t u d i e s o n th e i n t e r a c t i o n o f

H g B r 2 w i t h I m t a n d i t s d e r i v a t i v e s . A l s o t h e D i a z

a n d D i a p c o m p l e x e s o f H gC 12 a n d H g B r 2 a re a l s o

r e p o r t e d t o s e e t h e e f f e c t o f t h e s ix - a n d s e v e n -

m e m b e r e d r in g o n t h e 1 99 Hg N M R c h e m i c a l s h if ts ,

a l o n g w i t h I H a n d ~3C N M R s t u di e s .

O H

H / U ' H

Imt iaz Oiaz OH) Diap

a - h ) 0 j ) k )

C o m p l e x e s o f t h e f o l l o w i n g li g a n d s a r e r e p o r t e d :

( a ) R = R = H = i m i d a z o l i d i n e - 2 - t h i o n e ( I m t ) :

* Au thor to wh om co rrespondence should be addressed .

(b ) R

= CH 3

a n d R = H = N - m e t h y l - im i d -

a z o li d in e - 2 -t h io n e ( M e l m t ) ; (c ) R = - - C 2 H 5 a n d

R = H = N - e t h y l - i m i d a z o l i d i n e - 2 - t h i o n e

( E t I m t ) ; ( d ) R = - - C 3 H 7 a n d R t = H = N - p r o p y l -

i m i d a z o l id i n e - 2 - th i o n e ( P r I m t ) ; ( e) R = - - i - C 3 H 7

a n d R = H = N - i s o p r o p y l - i m i d a z o l i d i n e - 2 - t h io n e

( i - P r Im t ) ; ( f) R = R = - - C H 3 = N , N - d i m e t h y l -

i m i d a z o l i d i n e - 2 - t h i o n e ( D i M e t I m t ) ; ( g ) R = R =

C 2H 5 = N , N - d i e t h y l - i m i d a z o l i d i n e - 2 - t h i o n e

( D i E t l m t ) ; ( h) R = R = - - C ~ H 7 = N , N - d i is o -

p r o y l - i m i d a z o l i d i n e - 2 - t h i o n e ( D i - i - P r l m t ) ; ( i ) 1 , 3 -

d i a z i n a n e - 2 - t h i o n e ; ( j) 5 ( O H ) - l , 3 - d i a z i n a n e - 2 -

t h i o n e ; ( k ) 1 , 3 - d i a z i p a n e - 2 - t h i o n e .

E X P E R I M E N T A L

Chemicals

A l l t h e l i g a n d s h e r e w e r e p r e p a r e d b y t h e l i t e r a -

t u r e m e t h o d s . ~ t J ~ A n a l y t i c a l g r a d e H g C 1 2 , H g B r 2

a n d D M S O - d 6 w e r e o b t a i n e d f r o m t h e F l u k a

C h e m i c a l C o .

Preparation o[ the complexes

A l l t h e H g C 1 2 a n d H g B r 2 c o m p l e x e s w e r e p r e -

p a r e d a s d e s c r i b e d e a r li e r . 9 T h e e l e m e n t a l a n a l y s e s

o f t h e p r o d u c t s w e r e c a r r ie d o u t o n a C a r l o E r b a

( I t a l y ) e l e m e n t a l a n a l y s e r a n d a r e g i v e n in T a b l e 1 .

2397



2398 A . A . IS A B and H . P . P ER ZA N O W S K I

Table 1 . Analyt ical data for the L2HgX2 complexes

Com plex M .p t ( °C) Co lou r H (%) C (%) N (%)

(Imt)2HgB r2 236 W hite po w de r 1.9 (2.1) 11.8 (12.7) 9.3 (9.9)

(MeImt)2HgBr2 137 W hite pow der 2.4 (2.7) 15.0 (16.2) 8.9 (9.5)

(Etlmt)2HgBr2 127 W hite pow der 2.9 (3.2) 18.5 (19.3) 8.9 (9.0)

(PrImt)2HgBr2 98 W hite po wd er 3.5 (3.7) 21.9 (22.2) 8.7 (8.6)

(i-PrImt)2HgBr2 137 W hite po w de r 3.4 (3.7) 21.3 (22.2) 8.2 (8.6)

(DiM etImt)z HgB rz 141 W hite pow der 2.6 (3.2) 16.1 (19.3) 9.1 (9.0)

(DiEtImt)2HgBr2 94 W hite po wd er 3.9 (4.1) 24.0 (24.8) 8.0 (8.3)

(Di- i -PrImt)zHgBr2 145 W hite pow der 4.7 (4.9) 27.8 (29.5) 7.6 (7.7)

(Diaz)zHgC l2 178 Silver po wd er 3.4 (3.0) 18.4 (18.1) 10.6 (10.5)

(Diaz)2HgBr2 99 W hite pow der 2.7 (2.7) 15.9 (16.2) 9.6 (9.4)

(Diaz-OH)2HgC12 164 Bro wn pow de r 3.2 (2.6) 19.1 (18.0) 11.9 (10.5)

(Diaz-OH)2HgBr2 152 W hite pow der 2.2 (2.3) 14.8 (15.4) 8.5 (9.0)

(Diap)zHgC12 172 W hite po w de r 3.2 (2.6) 19.1 (18.0) 11.8 (10.5)

(Diap)zHgBr2 136 W hite pow der 3.0 (3.2) 18.4 (19.3) 8.8 (9.0)

The corresponding calculated values are given in parentheses.

N M R m e a s ur e m en t s

~H a n d ~3C N M R s p e c t r a w e r e m e a s u r e d o n a

B r u k e r A C - 8 0 s p e c t r o m e t e r a t 8 0 a n d 2 0 M H z ,

r e s p e ct i v e ly . A 0 . 15 M s o l u t i o n o f e a c h s a m p l e w a s

p r e p a r e d i n D M S O - d 6 . A l l t h e

1H

a n d

3C

N M R

s p e c t r a w e r e r e f e r e n c e d t o i n t e r n a l 1 , 4 - d i o x a n e

w h o s e I H a n d 13C p e a k s w e r e a s s ig n e d v a l u e s o f

+ 3 . 5 7 a n d + 6 7 . 4 p p m , r e sp e c ti v el y , c o m p a r e d

w i t h 0 . 0 0 p p m f o r T M S . I n c e r t a i n c a s e s , t h e ~ 3 C

N M R r e s o n a n c e o f s o m e l ig a n d s o v e r la p p e d w i th

D M S O - d 6 s o l v e n t r e s o n a n c e s . T h e D E P T t e c h -

n i q u e w a s u s e d t o r e s o l v e t h e c h e m i c a l s h i ft s o f t h e

o v e r l a p p i n g r e s o n a n c e s . ~ 99 Hg N M R s p e c t r a w e r e

m e a s u r e d a t 3 5 .7 8 4 M H z o n a V a r i a n X L - 2 0 0 s p e c-

t r o m e t e r . T h e

199Hg

i s o t o p e h a s I = 1 /2 , a n a t u r a l

a b u n d a n c e o f 1 6 . 9 % a n d s e n s it i vi t y o f 1 . 4% c o m -

p a r e d w i t h 1 0 0 % f o r p r o t o n . T h e f o l l o w in g c o n -

d i t i o n s w e r e u s e d : p u l s e w i d t h 8 . 0 / ~ s ( 9 0 ° ) , p u l s e

d e l a y 2 s , 3 2 K d a t a p o i n t s , s p e c t r a l w i d t h 5 0 , 0 0 0

H z , 1 0 m m m u l t i - n u c l e a r p r o b e , ~ H n o i s e d e c o u p -

l i n g a n d i n t e r n a l l o c k o n t h e d e u t e r i u m s i g n a l o f

t h e s o l v e n t . C h e m i c a l s h i f t s f o r W 9 H g w e r e c o m -

p u t e d w i t h r e f e r e n c e t o ( C H 3 ) 2 H g a t 0. 0 p p m a n d

c h e c k e d a g a i n s t e x t e r n a l H g C I 2 (1 M ) i n D M S O - d 6

s o l v e n t ( - - 1 5 01

p p m . 12A3

R S U L T S A N D D I S C U S S I O N

C o m p l e x a t i o n o f i m i d a z o l i d i n e - 2 - t h i o n e , 1 ,3 -

d i a z i n a n e - 2 - t h i o n e a n d 1 , 3 - d i a z e p in e - 2 - t h io n e w i t h

H gC 12 a n d H g B r 2 i n m o s t c a s e s g a v e w h i t e p o w d e r s

o r c r y s t a l l i n e p r o d u c t s . T h e a n a l y t i c a l d a t a a n d

s o m e p h y s i c a l p r o p e r t i e s o f th e c o m p l e x e s a r e l i s te d

i n T a b l e 1 .

I a n d

13C

N M R s t u di es

T h e 1H N M R s p e c t ra o f li g an d s a n d t h e c o m -

p l e x es w e r e m e a s u r e d . T h e c h e m i c a l s h i f ts o f t h e

N H p r o t o n o f th e i m i d a z o le r in g w e r e o b se r v e d

b e t w e e n 7 . 60 a n d 8 . 00 p p m f o r a ll li g a nd s . A f t e r

c o m p l e x i n g w i th H g C12 a n d H g B r 2 th e N H p r o t o n

w a s s h i f te d b y 0 . 8 0 - 1 .2 0 p p m f o r m o s t o f th e c o m -

p l e xe s . T h i s o b s e r v a t i o n i n d i c a t e s t h a t m e r c u r y ( I I )

i s n o t b o n d e d t h r o u g h t h e N H b i n d i n g s i te , i f i t

w e r e th e n N H r e s o n a n c e w o u l d n o t b e o b s e r v ed i n

t h e IH N M R s p e c t ro s c o p y .

T h e 13C N M R c h e m i c a l s h i ft s f o r t h e I m t a n d i ts

H gC 12 a n d H g B r 2 c o m p l e x e s w e r e m e a s u r e d . D i a z

a n d D i a p c o m p l e x e s w i t h H g C I2 a n d H g B r 2 w e r e

a l s o m e a s u r e d a n d t h e i r 1H a n d 13C N M R c h e m i c a l

s h if t s a r e a v a i l a b le o n r e q u e s t. T h e c a r b o n n e a r e s t

t o s u l f u r i s e x p e c t e d t o b e t h e m o s t s e n s i t i v e t o

c o o r d i n a t i o n t o m e t a l i o n s . A s e x p e c t e d , t h e C ( 2 )

c a r b o n i s s h if te d u p fi e ld b y - 6 . 2 9 t o - 7 . 4 0 p p m

f o r H g B r 2 c o m p l e x e s o f t h e N H s u b s t i t u t e d t h i o n e .

T h e H g C I 2 c o m p l e x e s o f th e s a m e l i g a n d s w e r e

s h if te d b y - 6 . 3 0 t o - 6 . 7 1 p p m . F o r t h e d i su b -

s t i tu t e d c o m p l e x e s o f H g B r 2 , t h e C ( 2 ) r e s o n a n c e

w a s s h i f t e d b y - 6 . 2 9 t o - 7 . 4 0 p p m a n d f o r H g C I 2

c o m p l e x e s o f t h e s a m e li g a n d s sh i f te d b y - 4 . 9 9 t o

- 5 .41 pp m .

I t s h o u ld b e n o t e d h e r e t h a t f o r N , N ' - d i s u b -

s t i tu t e d c o m p l e x e s o f H g C1 2 a n d H g B r 2 , t h e c h e m i -

c a l s h i ft d i f fe r e n c e b e t w e e n t h e f r e e a n d b o u n d

l i g a n d s i s s m a l l e r c o m p a r e d w i t h m o n o - s u b s t i t u t e d

c o m p l e x e s . T h i s i s b e c a u s e a l l l i g a n d s a r e i n t h e

t h i o n e f o r m ] 4-16 T h e t h i o n e g r o u p is a h a r d e r b a s e

t h a n t h e t h i o l a t e g r o u p , t h e r e f o r e , t h e i n t e r a c t i o n

b e t w e e n H g 2+ w h i c h i s a s o f t e r a c i d a n d t h e t h i o n e



NMR of--NHCS-containing ligands

Table 2.

99Hg

NMR chemical shifts (ppm) for the L2HgX2 complexes

Compound X = C1 X = Br- A

(Imt)zHgX2 -8 63.7 (77 Hz) - 1272.0 (1000 Hz) -408.3

(Melmt)zHgX2 -916.8 (51 Hz) - 1382.9 (54 Hz) -466.1

(Prlmt)2HgX2 -9 19.6 (83 Hz) - 1333.5 (150 Hz) -413.9

(i-Prlmt)2HgX2 -900.5 (65 Hz) - 1327.6 (260 Hz) -427.1

(DiMelmt)2HgX2 -970.5 (52 Hz) -1342.0 (450 Hz) -371.3

(DiEtlmt)2HgX: -995.7 (61 Hz) - 1407.3 (170 Hz) -411.6

(Di-i-Prlmt)2HgX2 - 1007.8 (109 Hz) - 1394.0 (480 Hz) -386. 0

L2HgCI2-L2HgBr2 (the chemical shifts difference in ppm).

2399

group is weaker compared with the thiolate group

and, therefore, the chemical shift difference between

the free and bound ligand is smaller. As indicated

in the Table 1, all the complexes are tetrahedral in

natu re and the H g 2+ is bon ded to the ligand via the

thione group only. 16 2o

1~9Hg N M R s t u di es

The 199Hg N MR chemica l shifts are listed in

Table 2 for the complexes of Imt and its derivatives

and in Table 3 for Diaz and Diap complexes of

HgCI2 and HgBr2.

As note d in Tables 2 and 3, all the complexes gave

a single resonance, however, some of the resonances

are extremely broad, e.g. (Imt)zHgBr2 has a Av~/2 of

1000 Hz compared with the (Imt)zHgC12 complex.

This broadening may be due to exchange of bound

and uncomplexed ligands. All the bromide com-

plexes are more negative than their analogous

chloride complexes, this reflects the electro-

negativity of the Br- ion. The HgC12 has a res-

onance at -1501.0 ppm, which shifts to -863.7

ppm, for (Imt)2HgC12 and the total difference is

637.3 ppm. For (Di-i-PrImt)2HgCl2 the difference

is only 493.2 ppm. This indicates the Imt is forming

a stronger complex than (Di-i-PrImt)2HgC12. This

observation is expected because the Imt ligand can

form a thiol ¢:-thi one equilibrium and after com-

plexation with the metal, it may shift to the thiolate

form, which is a softer base and thus form a stronger

compl ex tha n the thione . 7 The same is reflected for

the C(2) resonance shifts between free and bound

ligands. For (lmt)2HgC12 the C(2) shift is -6.71

ppm, whereas for (Di-i-Prlmt)2HgC12 the shift is

only - 4.99 ppm.

Another striking feature in Table 2 is the differ-

ence in chemical shift between HgCI2 and HgBr2

complexes as noted as A (delta). Note the highest

difference is - 466.1 ppm for MeI mt complexes and

the lowest difference is -371.3 ppm for DiMelmt

complexes.

These differences can be explained in terms of

bondi ng of the thione to the metal. Whe n one of the

NH groups is replaced by NR (where R = methyl

group), it may disturb the tetrahedral nature of the

complex because of the steric effect. Also, when

both NH and N'H are replaced by NR and N'R

(where R = methyl group), again the steric effect

will influence the tetrahedral nature of the complex

and since both sides are balanced by the same group

the steric effect will be bala nced and, therefore, have

less effect on t99Hg chemical shifts. When the

R group becomes larger, e.g. ethyl, propyl, iso-

propyl, etc., the chemical shift becomes less

sensitive.

Table 3.

L99Hg

NMR chemical shifts (ppm) for the L2HgX:-type complexes

(where L = 1,3-diazinane-2-thione or 1,3-diazepine-2-thione)

Compound L2HgC12 L2HgBr2 A

HgX2 - 1501.0 - 2069.7 - 568.7

(Diaz)2HgX2 - 805.6 (176 Hz) ~ - 1162.0 ( 1200 Hz) h - 356.4

(Diaz-OH)zHgX2 - 785.9 (223 Hz) - 1156.0 (V.broad) - 370.1

(Diap)2HgX2 -831.0 (143 Hz)

L2HgC12--L2HgBr2 (the chemical shift difference in ppm).

b A y I 2

(the line-width at the half height of the resonance).

' The resonance of (Diap)2HgBr2 is extremely broad.



2 40 0 A . A . I S A B a n d H .

A s n o t e d i n T a b l e 3 , t h e s i m i l a r

99Hg

N M R

c h e m i c a l s h i f t d i f f e r e n c e s b e t w e e n f r e e a n d b o u n d

D i a z c o m p l e x e s o f H gC 12 a n d H g B r 2 w e r e o b s e r v e d .

U n f o r t u n a t e l y , t h e ( D i a p ) 2 H g B r 2 99HgN M R r e s -

o n a n c e w a s e x tr e m e l y b r o a d a n d t h e re f o r e c a n n o t

b e c o m p a r e d w i t h it s a n a l o g o u s ( D ia p )2 H g C 12

99Hg

N M R r e s o n a n c e .

I n T a b l e 4 , w e a t t e m p t e d t o r e l at e t h e

99Hg

N M R

s h i ft s w i t h t h e s iz e o f th e l ig a n d s . F o r t h e H g C I 2

c o m p l e x e s o f I m t , D i a z a n d D i a p , i t is n o t a l in e a r

r e l a t i o n s h i p , e . g . t h e D i a z c o m p l e x s h i f t e d m o r e

t h a n t h e I m t a n d D i a p c o m p l e x e s. H o w e v e r , f o r

H g B r 2 t h e D i a z c o m p l e x s h if te d m o r e t h a n t h e I m t

c o m p l e x .

C a r t y et al. 19 s t u d i e d t h e c o m p l e x a t i o n o f

M e H g C N a n d c y s te i n e as w e ll as p e n ic i ll a m i n e i n

a q u e o u s s o l u t i o n . T h e

99Hg

N M R c h e m i c al s h if t

f o r M e H g C N w a s o b s e rv e d at - 7 44 p p m a n d a f te r

c o m p l e x i n g w i t h c y s t e in e , t h e r e s o n a n c e w a s s h i ft e d

t o - 5 5 7 p p m . H o w e v e r , a ft e r c o m p l e x i n g w i th

p e n i c il la m i n e i t s h if te d to - 5 3 8 p p m . T h e t o t a l

s h if ts w e r e - 1 8 7 a n d - 2 0 6 p p m , r e s p ec t iv e l y.

S i m i l a r c h e m i c a l s h i f t r a n g e s w e r e o b s e r v e d f o r

c y s te i n e p e p t id e s b o u n d t o H g n ? °

R e i d a n d R a b e n s t e i n 21 h a v e r e p o r t e d t h e f o r -

m a t i o n c o n s t a n ts f o r C H 3 H g - c y st e in e a n d C H 3 H g -

p e n i c i l l a m i n e a s 1 6 . 6 7 a n d 1 6 . 9 4 , r e s p e c t i v e l y . B o t h

t h e s e s t u d i e s i n d i c a t e t h a t t h e

99Hg

c h e m i c a l s h i f t

i s d i r e c t l y r e l a t e d t o t h e f o r m a t i o n o f c o m p l e x e s .

T h e s t r o n g e r b o n d i n g w i ll h a v e l a r g e r c h e m i c a l s h if t

d i f f e r e n c e b e t w e e n f r e e a n d b o u n d 99Hgc h e m i c a l

s h i f t s .

S h u n m u g a m et al. 16 s t u di e d t h e c o m p l e x a t i o n o f

2 - p y r i d i n e th i o n e a n d 4 - p y r i d i n e t h io n e w i t h Z n ,

C d n a n d H g II h a l i d e s b y I H a n d 13C N M R s p e c -

t r o s c o p y . T h e C ( 2 ) r e s o n a n c e f o r b o t h o f t h es e

l i g a n d s s h o w s t h e g r e a t e r s h i f t f o r t h e M B r 2 ( w h e r e

M = Z n 2 ÷, C d 2+ a n d H g 2 ÷ ) t h a n M C 12 c o m p l e x e s ,

e . g . f o r Z nL 2 C1 2 ( - 1 . 80 p p m ) a n d Z n L 2 B r 2 ( - 2 . 4 0

p p m ) , w h e r e L = 2 - p y r i d i n e th i o n e . F o r C d L 2 C I 2

( - 3 . 8 0 p p m ) a n d Cd Lz Br 2 ( - 4 . 9 0 p p m ) , f o r

H g L2 C 12 ( - 8 . 9 0 p p m ) a n d H g L 2 B r 2 ( - 1 0 .3 0 p p m ) .

A s i m i l a r o b s e r v a t i o n w a s m a d e f o r 4 - p y ri d in e

Tab l e 4 .

99Hg

N M R chem i ca l s h i ft s fo r Im t ,

D i a z a n d D i a p c o m p l e x e s

C o m p o u n d X = C I - X = B r

H g X 2 - 1 5 0 1 . 0 - - 20 6 9 .7

(Im t) ~HgX2 - 863.7 -- 1272.0

(Diaz)zHgX z - 805.6 - 1162.0

(Diap)2HgX2 - 831.0 a

~The resonance of (Diap)2HgBr2 i s

ex t r em el y b road .

P. P E R Z A N O W S K I

t h i o n e . I n t h e p r e s e n t s t u d y , w e a l s o o b s e r v e t h a t

f o r th e H g ( I m t ) 2 B r 2 c o m p l e x , t h e C ( 2 ) h a s a g r e a t e r

s h i ft t h a n t h e H g ( Im t ) 2 C 12 c o m p l e x . T h i s i s p r o b -

a b l y b e c a u s e b r o m i n e i s a b i g g e r a t o m a n d t h e d ,

p ~ b o n d i n g i s s t ro n g e r f o r H g - - B r c o m p a r e d w i t h

H g - - C 1 c o m p l e x e s , w h ic h i n tu r n s h o w t h e g r e a te r

C ( 2 ) r e s o n a n c e s h if t f o r H g B r2 c o m p l e x e s t h a n

HgC12.

A s i m il a r o b s e r v a t i o n w a s m a d e f o r im i d -

a z o l i d i n e - 2 - t h i o n e a n d C u H , Z n II, C d II a n d H g n

co m pl ex es . ~6

T h e r e s u l t s p r e s e n t e d h e r e s h o w t h a t I H , ~3C a n d

99HgN M R c h e m i ca l sh if ts ar e c o m p l e m e n t a r y a n d

t h e y p r o v i d e u s e f u l i n f o r m a t i o n o n t h e n a t u r e o f

t h e b o n d i n g . A l s o , t h e

99Hg

N M R c h e m i ca l s h if t

r a n g e i s v e r y l a r g e a n d t h e

99Hg resonan ces

a r e

s i n g l e t s f o r a l l t h e c o m p l e x e s . T h e c h e m i c a l s h i f t s

f o r d i f f e r e n t c o m p l e x e s p r e s e n t e d h e r e a r e u s e -

f u l e s p e c i a l l y i f t h e

99Hg

i s u s e d f o r b i o l o g i c a l

l i g a n d s b i n d i n g t o v a r i o u s m e r c u r y - c o n t a i n i n g

co m pl ex es . 22-24

Acknowledgements--This r e s ea rch was s uppo r t ed b y t he

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IH, 13C AND 199Hg NMR STUDIES OF THE --NHCSCONTAINING