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Pollhedron V o l
Pergamon
0277-5387(95)00505-6
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)
2397
2398
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)
N M R measurements
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
(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
A"
-408.3
-466.1
-413.9
-427.1
-371.3
-411.6
-386.0
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.
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)
A"
- 568.7
- 356.4
- 370.1
2400
Table 4.
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
is
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