8/20/2019 IH, 13C AND 199Hg NMR STUDIES OF THE --NHCSCONTAINING http://slidepdf.com/reader/full/ih-13c-and-199hg-nmr-studies-of-the-nhcscontaining 1/5 Pergamon 0277-5387 95)00505-6 ollhedron Vol 15. No 14. pp. 2:~97 2401, 1996 Copyright i 1996 Elsevier Science Ltd Printed in Great Britain. All rights reserved 11277 538796 150 0+0 00 IH 3C AND 199Hg NMR STUDIES OF THE --NHCS- CONTAINING LIGANDS WITH MERCURIC HALIDES ANVARHUSEIN A. ISAB* and HERMAN P. PERZANOWSKi Department of Chemistry, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia Received 12 July 1995, accepted 5 October 1995) Abstraet--The reaction of mercury(II) halides with imidazolidine-2-thione, 1,3-diazinane- 2-thione and 1,3-diazepine-2-thione yielded complexes of stoichiometry HgL2CI2 and HgL2Br2. The C(2) resonance of all thione ligands shifted more for HgBr2 complexes compared with HgC12. The 199Hg NMR chemical shift range is within -805 to - 1008 ppm for HgL2CI2 complexes and -1124 to -1394 ppm for all HgL2Br2 complexes. Also ~C and 199Hg NMR chemical shifts are compared for five-, six- and seven-membered ligands after complexing with mercuric halides. Copyright :( 1996 Elsevier Science Ltd. The coordination chemistry of the thioamido group --NHCS in heterocyclic penta-, hexa- and hepta- atomic rings, such as imidazolidine-2-thione (Imt), 1,3-diazinane-2-thione (Diaz) and 1,3-diazepine-2- thione (Diap) has been the subject of several recent studies. ~ 9 In our previous studies we reported the ~H, 13C and ~99Hg NMR studies of the complexation of HgCI2 by Imt and its derivatives. 9 It was found that ~99Hg chemical shifts are sensitive to the different substituents on the NH, N H imidazole ring. In this paper, we extend our studies on the interaction of HgBr2 with Imt and its derivatives. Also the Diaz and Diap complexes of HgC12 and HgBr2 are also reported to see the effect of the six- and seven- membered ring on the 199Hg NMR chemical shifts, along with IH and ~3C NMR studies. OH H/ U'H Imt iaz Oiaz OH) Diap a-h) 0 j) k) Complexes of the following ligands are reported : (a) R = R = H = imidazolidine-2-thione (Imt) : * Author to whom correspondence should be addressed. (b) R = CH 3 and R = H = N-methyl-imid- azolidine-2-thione (Melmt); (c) R =--C2H5 and R = H = N-ethyl-imidazolidine-2-thione (EtImt) ; (d) R = --C3H7 and R t = H = N-propyl- imidazolidine-2-thione (PrImt) ; (e) R =--i-C3H7 and R = H = N-isopropyl-imidazolidine-2-thione (i-PrImt) ; (f) R = R = --CH3 = N,N -dimethyl- imidazolidine-2-thione (DiMetIm t) ; (g) R = R = C2H5 = N,N -diethyl-imidazolidine-2-thione (DiEtlmt); (h) R = R =--C~H7 = N,N -diiso- proyl-imidazolidine-2-thione (Di-i-Prlmt); (i) 1,3- diazinane-2-thione; (j) 5 (OH)-l,3-diazinane-2- thione; (k) 1,3-diazipane-2-thione. EXPERIMENTAL Chemicals All the ligands here were prepared by the litera- ture methods.~tJ~ Analytical grade HgC12, HgBr2 and DMSO-d6 were obtained from the Fluka Chemical Co. Preparation o[ the complexes All the HgC12 and HgBr2 complexes were pre- pared as described earlier. 9 The elemental analyses of the products were carried out on a Carlo Erba (Italy) elemental analyser and are given in Table 1. 2397
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IH, 13C AND 199Hg NMR STUDIES OF THE --NHCSCONTAINING
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8/20/2019 IH, 13C AND 199Hg NMR STUDIES OF THE --NHCSCONTAINING
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
8/20/2019 IH, 13C AND 199Hg NMR STUDIES OF THE --NHCSCONTAINING