~

Pollhedron V o l

15. N o 14. pp. 2:~97 2401, 1996

Copyright i 1996 Elsevier Science Ltd
Printed in Great Britain. All rights reserved
11277 538796 $ 1 5 0 0 + 0 0 0

Pergamon
0277-5387(95)00505-6

IH, 13C A N D 199Hg N M R S T U D I E S OF THE - - N H C S C O N T A I N I N G LIGANDS WITH M E R C U R I C 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)

A b s t r a e t - - T h e reaction of mercury(II) halides with imidazolidine-2-thione, 1,3-diazinane2-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 N M R chemical shift range is within - 8 0 5 to - 1008 ppm
for HgL2CI2 complexes and - 1 1 2 4 to - 1 3 9 4 p p m for all HgL2Br2 complexes. Also ~C
and 199Hg N M R 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

- - N H C S in heterocyclic penta-, hexa- and heptaatomic rings, such as imidazolidine-2-thione (Imt),
1,3-diazinane-2-thione (Diaz) and 1,3-diazepine-2thione (Diap) has been the subject of several recent
studies. ~ 9
In our previous studies we reported the ~H, 13C
and ~99Hg N M R 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 sevenmembered ring on the 199Hg N M R chemical shifts,
along with IH and ~3C N M R studies.

(b) R = - - C H 3 and R ' = H = N-methyl-imidazolidine-2-thione (Melmt); (c) R = - - C 2 H 5 and

R' = H = N-ethyl-imidazolidine-2-thione
(EtImt) ; (d) R = --C3H7 and R t = H = N-propylimidazolidine-2-thione (PrImt) ; (e) R = - - i - C 3 H 7
and R' = H = N-isopropyl-imidazolidine-2-thione
(i-PrImt) ; (f) R = R' = - - C H 3 = N,N'-dimethylimidazolidine-2-thione (DiMetImt) ; (g) R = R' =
C2H5 = 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
(DiEtlmt); (h) R = R' = - - C ~ H 7 = N,N'-diisoproyl-imidazolidine-2-thione (Di-i-Prlmt); (i) 1,3diazinane-2-thione; (j) 5'(OH)-l,3-diazinane-2thione; (k) 1,3-diazipane-2-thione.

EXPERIMENTAL

Chemicals

OH

All the ligands here were prepared by the literature methods.~tJ~ Analytical grade HgC12, HgBr2
and DMSO-d6 were obtained from the Fluka
Chemical Co.

H/"U'H
Imt

Diaz

(a-h)

(0

Oiaz(OH)
(j)

Diap
(k)

Complexes of the following ligands are reported :

(a) R = R' = H = imidazolidine-2-thione (Imt) :

* Author to whom correspondence should be addressed.

Preparation o[ the complexes

All the HgC12 and HgBr2 complexes were prepared 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

2398

A. A. ISAB and H. P. PERZANOWSKI

Table 1. Analytical data for the L2HgX2 complexes"
Complex
(Imt)2HgBr2
(MeImt)2HgBr2
(Etlmt)2HgBr2
(PrImt)2HgBr2
(i-PrImt)2HgBr2
(DiMetImt)zHgBrz
(DiEtImt)2HgBr2
(Di-i-PrImt)zHgBr2
(Diaz)zHgCl2
(Diaz)2HgBr2
(Diaz-OH)2HgC12
(Diaz-OH)2HgBr2
(Diap)zHgC12
(Diap)zHgBr2

M.pt (C)
236
137
127
98
137
141
94
145
178
99
164
152
172
136

Colour
White powder
White powder
White powder
White powder
White powder
White powder
White powder
White powder
Silver powder
White powder
Brown powder
White powder
White powder
White powder

H (%)

C (%)

N (%)

1.9 (2.1)
2.4 (2.7)
2.9 (3.2)
3.5 (3.7)
3.4 (3.7)
2.6 (3.2)
3.9 (4.1)
4.7 (4.9)
3.4 (3.0)
2.7 (2.7)
3.2 (2.6)
2.2 (2.3)
3.2 (2.6)
3.0 (3.2)

11.8 (12.7)
15.0 (16.2)
18.5 (19.3)
21.9 (22.2)
21.3 (22.2)
16.1 (19.3)
24.0 (24.8)
27.8 (29.5)
18.4 (18.1)
15.9 (16.2)
19.1 (18.0)
14.8 (15.4)
19.1 (18.0)
18.4 (19.3)

9.3 (9.9)
8.9 (9.5)
8.9 (9.0)
8.7 (8.6)
8.2 (8.6)
9.1 (9.0)
8.0 (8.3)
7.6 (7.7)
10.6 (10.5)
9.6 (9.4)
11.9 (10.5)
8.5 (9.0)
11.8 (10.5)
8.8 (9.0)

The corresponding calculated values are given in parentheses.

N M R measurements

IH and 13C N M R studies

~H and ~3C N M R spectra were measured on a

Bruker AC-80 spectrometer at 80 and 20 MHz,
respectively. A 0.15 M solution of each sample was
prepared in DMSO-d6. All the 1H and 13C N M R
spectra were referenced to internal 1,4-dioxane
whose IH and 13C peaks were assigned values of
+3.57 and +67.4 ppm, respectively, compared
with 0.00 ppm for TMS. In certain cases, the ~3C
N M R resonance of some ligands overlapped with
DMSO-d6 solvent resonances. The D E P T technique was used to resolve the chemical shifts of the
overlapping resonances. ~99Hg N M R spectra were
measured at 35.784 MHz on a Varian XL-200 spectrometer. The 199Hg isotope has I = 1/2, a natural
abundance of 16.9% and sensitivity of 1.4% compared with 100% for proton. The following conditions were used: pulse width 8.0/~s (90), pulse
delay 2 s, 32 K data points, spectral width 50,000
Hz, 10 mm multi-nuclear probe, ~H noise decoupling and internal lock on the deuterium signal of
the solvent. Chemical shifts for W9Hg were computed with reference to (CH3)2Hg at 0.0 ppm and
checked against external HgCI2 (1 M) in DMSO-d6
solvent (-- 1501 ppm). 12A3

The 1H N M R spectra of ligands and the complexes were measured. The chemical shifts of the
N H proton of the imidazole ring were observed
between 7.60 and 8.00 ppm for all ligands. After
complexing with HgC12 and HgBr2 the N H proton
was shifted by 0.80-1.20 ppm for most of the complexes. This observation indicates that mercury(II)
is not bonded through the N H binding site, if it
were then N H resonance would not be observed in
the IH N M R spectroscopy.
The 13C N M R chemical shifts for the Imt and its
HgC12 and HgBr2 complexes were measured. Diaz
and Diap complexes with HgCI2 and HgBr 2 were
also measured and their 1H and 13C N M R chemical
shifts are available on request. The carbon nearest
to sulfur is expected to be the most sensitive to
coordination to metal ions. As expected, the C(2)
carbon is shifted upfield by - 6 . 2 9 to - 7 . 4 0 ppm
for HgBr2 complexes of the N H substituted thione.
The HgCI2 complexes of the same ligands were
shifted by - 6 . 3 0 to - 6 . 7 1 ppm. For the disubstituted complexes of HgBr2, the C(2) resonance
was shifted by - 6.29 to - 7.40 ppm and for HgCI2
complexes of the same ligands shifted by - 4 . 9 9 to
- 5.41 ppm.
It should be noted here that for N,N'-disubstituted complexes of HgC12 and HgBr2, the chemical shift difference between the free and bound
ligands is smaller compared with mono-substituted
complexes. This is because all ligands are in the
thione f o r m ] 4-16 The thione group is a harder base
than the thiolate group, therefore, the interaction
between Hg 2+ which is a softer acid and the thione

R E S U L T S AND D I S C U S S I O N

Complexation of imidazolidine-2-thione, 1,3diazinane-2-thione and 1,3-diazepine-2-thione with

HgC12 and HgBr2 in most cases gave white powders
or crystalline products. The analytical data and
some physical properties of the complexes are listed
in Table 1.

NMR of--NHCS-containing ligands

Table 2.
Compound

199HgNMR chemical shifts (ppm)

X = C1

(Imt)zHgX2
-863.7 (77 Hz)
(Melmt)zHgX2
-916.8 (51 Hz)
(Prlmt)2HgX2
-919.6 (83 Hz)
(i-Prlmt)2HgX2
-900.5 (65 Hz)
(DiMelmt)2HgX2
-970.5 (52 Hz)
(DiEtlmt)2HgX:
-995.7 (61 Hz)
(Di-i-Prlmt)2HgX2 - 1007.8 (109 Hz)

2399

for the L2HgX2complexes

X = Br-

- 1272.0 (1000 Hz)

- 1382.9 (54 Hz)
- 1333.5 (150 Hz)
- 1327.6 (260 Hz)
-1342.0 (450 Hz)
- 1407.3 (170 Hz)
- 1394.0 (480 Hz)

A"
-408.3
-466.1
-413.9
-427.1
-371.3
-411.6
-386.0

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

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
nature and the Hg 2+ is bonded to the ligand via the
thione group only. 16 2o
1~9Hg N M R studies
The 199Hg N M R chemical 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 noted 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 complexes are more negative than their analogous
chloride complexes, this reflects the electronegativity of the Br- ion. The HgC12 has a resonance at - 1 5 0 1 . 0 ppm, which shifts to - 8 6 3 . 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 :-thione equilibrium and after complexation with the metal, it may shift to the thiolate
form, which is a softer base and thus form a stronger
complex than 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 . 7 1
ppm, whereas for (Di-i-Prlmt)2HgC12 the shift is
only - 4.99 ppm.
Another striking feature in Table 2 is the difference in chemical shift between HgCI2 and HgBr2
complexes as noted as A (delta). Note the highest
difference is - 466.1 ppm for MeImt complexes and
the lowest difference is - 3 7 1 . 3 ppm for DiMelmt
complexes.
These differences can be explained in terms of
bonding of the thione to the metal. When one of the
N H groups is replaced by N R (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 N R 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 balanced and, therefore, have
less effect on t99Hg chemical shifts. When the
R group becomes larger, e.g. ethyl, propyl, isopropyl, etc., the chemical shift becomes less
sensitive.

Table 3. L99HgNMR chemical shifts (ppm) for the L2HgX:-type complexes

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

L2HgC12

HgX2
- 1501.0
(Diaz)2HgX2
- 805.6 (176 Hz) ~
(Diaz-OH)zHgX2 - 785.9 (223 Hz)
(Diap)2HgX2
-831.0 (143 Hz)

L2HgBr2
- 2069.7
- 1162.0 ( 1200 Hz) h
- 1156.0 (V.broad)

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

b AyI/2 (the line-width at the half height of the resonance).
' The resonance of (Diap)2HgBr2 is extremely broad.

A"
- 568.7
- 356.4
- 370.1

2400

A.A. ISAB and H. P. PERZANOWSKI

As noted in Table 3, the similar 199Hg N M R

chemical shift differences between free and bound
Diaz complexes of HgC12 and HgBr2 were observed.
Unfortunately, the (Diap)2HgBr2 199HgN M R resonance was extremely broad and therefore cannot
be compared with its analogous (Diap)2HgC12 199Hg
N M R resonance.
In Table 4, we attempted to relate the 199HgN M R
shifts with the size of the ligands. For the HgCI2
complexes of Imt, Diaz and Diap, it is not a linear
relationship, e.g. the Diaz complex shifted more
than the Imt and Diap complexes. However, for
HgBr2 the Diaz complex shifted more than the I m t
complex.
Carty et al. 19 studied the complexation of
M e H g C N and cysteine as well as penicillamine in
aqueous solution. The 199HgN M R chemical shift
for M e H g C N was observed at - 744 p p m and after
complexing with cysteine, the resonance was shifted
to - 5 5 7 ppm. However, after complexing with
penicillamine it shifted to - 5 3 8 ppm. The total
shifts were - 1 8 7 and - 2 0 6 ppm, respectively.
Similar chemical shift ranges were observed for
cysteine peptides bound to H g n ?
Reid and Rabenstein 21 have reported the formation constants for CH3Hg-cysteine and CH3Hgpenicillamine as 16.67 and 16.94, respectively. Both
these studies indicate that the 199Hgchemical shift
is directly related to the formation of complexes.
The stronger bonding will have larger chemical shift
difference between free and bound 199Hgchemical
shifts.
Shunmugam et al. 16 studied the complexation of
2-pyridinethione and 4-pyridinethione with Zn",
Cd n and Hg II halides by IH and 13C N M R spectroscopy. The C(2) resonance for both of these
ligands shows the greater shift for the MBr2 (where
M = Zn 2, Cd 2+ and Hg 2) than MC12 complexes,
e.g. for ZnL2C12 ( - 1.80 ppm) and ZnL2Br2 ( - 2.40
ppm), where L = 2-pyridine thione. F o r CdL2CI2
( - 3 . 8 0 ppm) and CdLzBr2 ( - 4 . 9 0 ppm), for
HgL2C12 ( - 8.90 ppm) and HgL2Br2 ( - 10.30 ppm).
A similar observation was made for 4-pyridine

Table 4.

199HgNMR chemical shifts for Imt,

Diaz and Diap complexes

Compound

X = CI-

X = Br

HgX 2
(Imt) ~HgX2
(Diaz)zHgXz
(Diap)2HgX2

- 1501.0
- 863.7
- 805.6
- 831.0

--2069.7
-- 1272.0
- 1162.0
a

~The resonance of (Diap)2HgBr2

extremely broad.

is

thione. In the present study, we also observe that

for the Hg(Imt)2Br2 complex, the C(2) has a greater
shift than the Hg(Imt)2C12 complex. This is probably because bromine is a bigger atom and the d,
p~ bonding is stronger for H g - - B r compared with
Hg--C1 complexes, which in turn show the greater
C(2) resonance shift for HgBr2 complexes than
HgC12.
A similar observation was made for imidazolidine-2-thione and Cu H, Zn II, Cd II and Hg n
complexes. ~6
The results presented here show that IH, ~3C and
199HgN M R chemical shifts are complementary and
they provide useful information on the nature of
the bonding. Also, the 199HgN M R chemical shift
range is very large and the 199Hg resonances are
singlets for all the complexes. The chemical shifts
for different complexes presented here are useful especially if the 199Hg is used for biological
ligands binding to various mercury-containing
complexes. 22-24
Acknowledgements--This research was supported by the

KFUPM Research Committee under the project No.

CY/CYANIDE/175.

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