Coordination compounds of tin and bismuth. Complexes of tin(IV) and bismuth(III) with N,N-dialkyldithiocarbamates

Article abstract of DOI:10.1081/SIM-100104783

Tin and bismuth metals react with N,N′,N′-tetraethylthiuramdisulfide, [Et₂NC(S)S]₂, and N,N,N′,N′-tetramethylthiuramdisulfide, [Mt₂NC(S)S]₂, in refluxing toluene to give the compounds Sn(S₂CNR₂)₄ (R = Et, Me) in high yield. Under similar conditions bismuth gives Bi(S₂CNR₂)₃. The reaction of metallic tin with a mixture of iodine and [R₂NC(S)S]₂ gives the compounds SnI(S₂CNR₂)₃, and SnI₂(S₂CNR₂)₂. Similarly, with mixtures of [R₂NC(S)S]₂ and I₂, bismuth yields BiI(S₂CNR₂)₂ and BiI₂(S₂CNR₂). Adducts of Bi(S₂CNR₂)₃ with 1,10-phenanthroline and 2,2′-bipyridyl were also prepared. The compounds and adducts were characterized by microanalyses, infrared, UV/Visible spectroscopy and conductivity measurements.

Full text of DOI:10.1081/SIM-100104783

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COORDINATION COMPOUNDS OF TIN AND BISMUTH.
COMPLEXES OF TIN(IV) AND BISMUTH(III) WITH N,N-
DIALKYLDITHIOCARBAMATES
I. A. Mustafa a & Amer A. Taqa b
a Chemistry Department, College of Science, University of Mosul, Mosul, Iraq
b Department of Dental Basic Science, College of Dentistry, University of Mosul, Mosul, Iraq
Version of record first published: 20 Aug 2006.
To cite this article: I. A. Mustafa & Amer A. Taqa (2001): COORDINATION COMPOUNDS OF TIN AND BISMUTH. COMPLEXES
OF TIN(IV) AND BISMUTH(III) WITH N,N-DIALKYLDITHIOCARBAMATES, Synthesis and Reactivity in Inorganic and Metal-Organic
Chemistry, 31:4, 517-526
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SYNTH. REACT. INORG. MET.-ORG. CHEM., 31(4), 517–526 (2001)
COORDINATION COMPOUNDS OF TIN
AND BISMUTH. COMPLEXES OF TIN(IV)
AND BISMUTH(III) WITH
N,N-DIALKYLDITHIOCARBAMATES
I. A. Mustafa1,* and Amer A. Taqa2
1Chemistry Department, College of Science, and
2Department of Dental Basic Science,
College of Dentistry, University of Mosul, Mosul, Iraq
ABSTRACT
Tin and bismuth metals react with N,N,N0,N0-tetraethyl-
thiuramdisulfide, [Et2NC(S)S]2, and N,N,N0,N0-tetramethyl-
thiuramdisulfide, [Mt2NC(S)S]2, in refluxing toluene to give
the compounds Sn(S2CNR2)4 (R ¼ Et, Me) in high yield.
Under similar conditions bismuth gives Bi(S2CNR2)3. The re-
action of metallic tin with a mixture of iodine and [R2NC(S)S]2
gives the compounds SnI(S2CNR2)3 and SnI2(S2CNR2)2.
Similarly, with mixtures of [R2NC(S)S]2 and I2, bismuth yields
BiI(S2CNR2)2 and BiI2(S2CNR2). Adducts of Bi(S2CNR2)3
with 1,10-phenanthroline and 2,20-bipyridyl were also pre-
pared. The compounds and adducts were characterized by
microanalyses, infrared, UV=Visible spectroscopy and con-
ductivity measurements.
*Corresponding author.
517
Copyright # 2001 by Marcel Dekker, Inc.
www.dekker.com

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MUSTAFA AND TAQA
INTRODUCTION
Interest in complexes of both main group and transition metals with
sulfur donor ligands arises in part because of their varied structures and
because of their biological activity1À6. Direct electrochemical syntheses were
used to prepare simple thiolato complexes of zinc, cadmium, mercury7,
lead8, indium and thallium9. An alternative route to the electrochemical
synthesis involves reaction between the disulfide ligand and the main group
metal in refluxing toluene6,10
.
Although many disulfide compounds are reduced by reaction with
metal ions via the oxidation of M(I) to M(III) (M ¼ Cu(I)11, In(I)12, Ir(I)
and Rh(I)13) or the use of Ni(II) under certain conditions14, this is not
always the case, some thiuramdisulfide compounds, [R2NC(S)S]2 (R ¼ Et or
Me), have been shown to coordinate unaltered15. However, disulfides of the
type [Et2NC(S)S]2 may be readily reduced by reaction with lead thiolates16
or with Rh[Ph2PC(S)NPh](PPh3)213. In this paper the oxidative addition of
the -S-S- linkage of [R2NC(S)S]2 (R ¼ Et or Me) to tin and bismuth metals,
reactions of thiuramdisulfide with different molar ratio of iodine and tin or
bismuth metal, are discussed. Also reported is the preparation of the bis-
muth compound adducts with the neutral donor bases 1,10-phenanthroline
(phen) and 2,20-bipyridyl (bipy).
EXPERIMENTAL
General Data
Tin and bismuth metals, [Me2NC(S)S]2, [Et2NC(S)S]2, toluene and
other reagent were used as supplied (Fluka). C, H, N microanalyses were
carried out using a 1106 Carlo Erba analyzer. Infrared spectra were recor-
ded on a Perkin-Elmer 580 infrared spectrophotometer using CsI pellets.
UV=Visible spectra were recorded on a UV=160 Shimadzu UV=Visible
recording spectrophotometer. Conductance measurements were carried out
at room temperature in DMF solution (1073 M) using a Jenway 4070
conductivity meter.
Syntheses
Sn(S2CNMe2)4 and Sn(S2CNEt2)4
A mixture of finely cut tin metal (0.119 g, 1 mg atom) and the disulfide
(2 mmol) in toluene (40 mL) was refluxed vigorously for 5 h. The mixture

TIN AND BISMUTH COMPLEXES
519
was evaporated in vacuo and the residue was triturated with n-pentane
(10 mL) to give an orange solid, which was collected by filtration and dried
in vacuo; yield 0.54 g for the methyl derivative and 0.62 g for the ethyl
derivative, respectively.
SnI(S2CNMe2)3 and SnI(S2CNEt2)3
A mixture of finely cut tin metal (0.119 g, 1 mg atom), the disulfide
(1.5 mmol) and iodine (0.127 g, 0.5 mmol) in toluene (30 mL) was refluxed
vigorously for 5 h. The mixture was filtered to remove traces of unreacted tin
metal (0.007 g). A yellow solid obtained after the volume of the filtrate was
reduced to ca.1=3 and cooled to room temperature. The solid was collected
and dried in vacuo; yields 0.50 g and 0.55 g, respectively.
SnI2(S2CNMe2)2 and SnI2(S2CNEt2)2
These were prepared by the same method as above except that 0.254 g
(1 mmol) of iodine was used along with the disulfide (1 mmol); yields 0.50 g
and 0.54 g, respectively.
Bi(S2CNMe2)3 and Bi(S2CNEt2)3
A mixture of small pieces of bismuth metal (0.21 g, 1 mg atom) and the
disulfide (1.5 mmol) in toluene (50 mL) were refluxed for 3 h. The unreacted
traces of bismuth (0.01 g) were removed by filtration, and the resultant
yellow solutions were reduced to ca. 1=3 of their volume and cooled to room
temperature. The solid obtained was then collected by filtration, washed
with petroleum ether (b.p. 60À80 ꢀC) and dried in vacuo; yields 0.50 g and
0.55 g, respectively.
BiI(S2CNMe2)2 and BiI(S2CNEt2)2
Small pieces of bismuth metal (0.21 g, 1 mg atom) were refluxed with
1.5 mmol of the disulfides and iodine (0.127 g, 0.5 mmol) in toluene (30 mL).
A yellow solution was formed after 3.5 h, after which time the solution was
filtered while hot to remove any traces of unreacted metal (0.01 g). The
collected solids were washed with petroleum ether (b.p. 60À80 ꢀC) and dried
in vacuo; yields 0.47 g and 0.53 g, respectively.

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MUSTAFA AND TAQA
BiI2(S2CNMe2) and BiI2(S2CNEt2)
These were prepared by the same method as above except that 0.254 g,
1 mmol iodine was used along with the disulfides (0.47 mmol); yields 0.47 g
and 0.52 g, respectively.
Bi(S2CNMe2)3.phen and Bi(SCNEt2)3.phen
The reaction of Bi(S2CNMe2)3 (0.57 g, 1 mmol) or Bi(S2CNEt2)3
(0.65 g, 1 mmol) and 1,10-phenathroline (phen) (0.18 g, 1 mmol) in methanol
(20 mL) yielded a yellow oil which became a solid after stirring for 4 h at
ambient temperature. This solid was collected, washed with methanol
(10 mL) and dried in vacuo; yields 0.61 g and 0.65 g, respectively.
Bi(S2CNMe2)3.bipy and Bi(S2CNEt2)3.bipy
Bi(S2CNMe2)3 (0.57 g, 1 mmol) or Bi(S2CNEt2)3 (0.65 g, 1 mmol) was
stirred with 2,20-bipyridine (bipy) (0.16 g, 1 mmol) in benzene (30 mL) for 3 h
during which time a deep yellow oil was formed. The colorless solution was
removed and the oil was triturated with diethylether (40 mL). The resultant
solid was dried in vacuo; yields 0.58 g and 0.63 g, respectively.
RESULTS AND DISCUSSION
The method described represents simple and direct syntheses of a
number of Sn(S2CNR2)4 and Bi(S2CNR2)3 compounds by thermal oxidative
addition reactions. These reactions are simpler than those used for the
preparation of M(S2CNR2)n compounds of main group elements involving
metathetical reactions17À19 of MXn with NaS2CNR2 or via the insertion of
CS2 into M(NR2)n20À22
.
The possible reaction involved is that shown in eq (1) giving a þ1
oxidation state species, which is then followed by the oxidative insertion
reaction of eq (2) or (3).
2M þ ½R2NCðSÞSŠ ! 2½MðS2CNR2ފ
ð1Þ
ð2Þ
2
2½MðS2CNR2ފ þ ðn À 1Þ½R2NCðSÞSŠ ! 2½MðS2CNR2ÞnŠ
2
2½MðS2CNR2ފþðnÀ1Þ½R2NCðSÞSŠ2 þmI2 !2½MImðS2CNR2ÞnŠ ð3Þ
BiðS2CNR2Þ3 þ phen or bipy ! BiðS2CNR2Þ3:phen or bipy ð4Þ

TIN AND BISMUTH COMPLEXES
521
The oxidative addition process of eqs (2) and (3) are clearly analogous
to known reactions involving the conversions23 Inð0Þ ! InðIIIÞ or SnðIIÞ !
SnðIVÞ.
The reaction of tris(N,N-dialkyldtiocarbamato)bismuth(III) com-
plexes, Bi(S2CNR2)3, with phen or bipy (1:1 molar ratio) yields neutral
adducts of stoichiometry Bi(S2CNR2)3.phen and Bi(S2CNR2)3.bipy respec-
tively [eq (4)].
The compounds and adducts were isolated as colored solids. Their
melting points, elemental analyses and conductivities are listed in Table I.
The important diagnostic bands of the IR spectra are listed in Table II.
The characteristic IR bands that are sensitive to molecular structure
are the stretching modes for the C-N, C-S and M-S bonds. In particular, the
n(C-N) band in the region 1450À1550 cm71 and the n(C-S) band in the
region 850À1050 cm71 are known to depend on the nature of the coordi-
nation of the dithiocarbamate ligands to the metal17,24. The splitting of
n(C-N) and n(C-S) bands is characteristic of a monodentate dithiocarba-
mate ligand whereas the appearance of a single band in each region
is characteristic of bidentate chelation of the dithiocarbamate ligand. The
dithiocarbamate ligands in Sn(S2CNR2)4, SnI(S2CNR2)3, Bi(S2-
CNR2)3.phen and Bi(S2CNR2)3.bipy act both as monodentate and as
bidentate ligands; the patterns for n(C-N) and n(C-S) are consistent with this
(Table II). The IR spectra of the compounds Bi(S2CNR2)3, BiI(S2CNR2)2
and BiI2(S2CNR2) show the pattern characteristic of bidentate dithio-
carbamate ligands. The IR spectra of the compounds SnI2(S2CNR2)2 show
the presence of two n(C-S) bands and one strong n(C-N) band. This is an
indication of the anisobidentate (unsymmetric) character of the dithio-
carbamate ligands17,25. Further support for the coordination of these deri-
vative was provided by the appearance of bands at about 320À390 cm71
which are assigned to n(Sn-S)26 and n(Bi-S)6, while the n(Bi-N) absorption
of the phen and bipy adducts are in good agreement with the reported values
for similar compounds which fall in the range6,27 220À270 cm71
.
It may be concluded that there is an octahedral geometry round the tin
atom in the present compounds of tin (Fig. 1). Hexa-coordinated com-
pounds of tin were described elsewhere17,28. On the other hand, bismuth is
hexa-coordinated in the complexes Bi(S2CNR2)3 and hexa- or hepta-coor-
dinated in Bi(S2CNR2)3.phen and Bi(S2CNR2)3-bipy. The coexistance in
one structure of a monodentate and a bidentate dithiocarbamate ligand has
been established earlier17,26
.
The adducts of Bi(S2CNR2)3 with phen or bipy might contain one or
two monodentate CSÀ2 groups, thus giving rise to the possibility of octa-
hedral or pentagonal-bipyramidal structures (Fig. 2). Compounds of hexa-
and hepta-coordinated bismuth were described elsewhere18À22
.

522
MUSTAFA AND TAQA

TIN AND BISMUTH COMPLEXES
523

524
MUSTAFA AND TAQA
Figure 1. Suggested structure of SnI(S2CNR2)3.
Figure 2. Suggested structure of Bi(S2CNR2)3.phen or bipy; (a) hepta-coordinated
bismuth or (b) hexa-coordinated bismuth.
The UV=Visible spectra of the compounds are similar to one another
(Table II). The band observed in the region 260À330 nm might be due
to p-p* transitions of the dithiocarbamate ligands, while an additional
band was observed for the compounds and the adducts in the range 380À
420 nm17,20,22. The new band was attributed to the charge transfer transition
from the ligand orbital to the vacant metal orbitals.
The molar conductivities of 107 3 M solutions of the compounds and
adducts indicate the non-electrolyte nature29 of these compounds and
adducts in DMF.

TIN AND BISMUTH COMPLEXES
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Received: January 10, 2000
Accepted: February 5, 2001
Referee I: R. S. Herrick
Referee II: E. Maslowski, Jr.