Formation of bismuth(V) thiolates: Protolysis and oxidation of triphenylbismuth(III) with heterocyclic thiols

Article abstract of DOI:10.1002/anie.201301200

Stressing bismuth: Two monophenyl tetrathiolato Bi^V complexes, [BiPh(SR)₄], have been prepared upon treating BiPh₃ in toluene/ethanol under reflux conditions with an excess of N-heterocyclic thiols (see scheme), indicating

Full text of DOI:10.1002/anie.201301200

Angewandte
Chemie
DOI: 10.1002/anie.201301200
Coordination Chemistry
Formation of Bismuth(V) Thiolates: Protolysis and Oxidation of
Triphenylbismuth(III) with Heterocyclic Thiols**
Ahmad Luqman, Victoria L. Blair, Alan M. Bond, and Philip C. Andrews*
Bismuth(V) compounds are strongly oxidizing[1] and in the
absence of stabilizing aryl groups remain extremely scarce.
The majority of compounds that show reasonable stability
and have been characterized in the solid state are heteroleptic
triarylbismuth(V) compounds of the form [BiAr3X2],[2] where
X is solely, or a combination of, aryl groups (Ar),[3] halides
(except iodide),[4] and anionic oxygen-based ligands; oxido,[5]
carboxylates,[6] sulfonates,[7] phenoxides,[8] or nitrate.[9] These
are all “hard” ligands, or in the case of aryl groups, are
calculated to have high group electronegativities.[10] Thus, the
neutral pentaarylbismuth(V) compounds, [BiAr5] (Ar= Ph,
p-Tol, C6F5, C6H3F2, or C6H4F), of which nine have thus far
been crystallographically characterized, are stable and often
highly colored.[2,3] In contrast, BiMe5 is unstable and explodes
on warming to room temperature.[11] In structural terms, the
majority of these compounds adopt a trigonal bipyramidal
geometry—[BiAr5] compounds being the notable excep-
tions—in which the more electronegative X ligands occupy
the axial positions. The low toxicity of bismuth, the strong
oxidizing nature of the complexes, the presence of an
electrophilic Bi center, and highly labile ligands, have all
contributed to a renewed interest in the role of triarylbis-
muth(V) complexes in organic synthesis.[12]
chemistry. To date, compounds of the type [BiAr5ꢀn(SR)n]
(n = 1–5) are unknown, most likely stemming from the “soft”
nature of the thiolate ligands and an inability to stabilize the
high charge on the BiV center. In fact, inorganic BiIII
compounds are known to promote disulfide formation from
thiols.[18] By studying various methods towards the synthesis
of novel biologically active bismuth thiolates, we now
describe the formation and characterization of the first
monoarylbismuth(V) thiolates, derived from 1-methyl-1H-
imidazole-2-thiol and 4-methyl-4H-1,2,4-triazole-3-thiol, and
their subsequent facile transformation into their reduced BiIII
congeners, the crystal structures of which retain the hallmarks
of their BiV origin.
Triphenylbismuth was treated with 4-methyl-4H-1,2,4-
triazole-3-thiol [4-MTT(H)] or 2-mercapto-1-methylimida-
zole [2-MMI(H)] in a toluene/ethanol solvent mixture at
reflux or by microwave (MW) irradiation, resulting in the
formation of a bright yellow solid in both cases (Scheme 1).
Diarylbismuth(V) compounds, [BiAr2X3], are less stable
than their triaryl counterparts, and are rare. Known examples
are: the oxido-cluster [Bi4(o-Tol)8O6],[13] and three complexes
supported and stabilized through internal coordination,
[Bi2(o-Et2NCH2-C6H4)4(CO3)],[14] [Bi2{(o-Me2NCH2)2
C6H3}4O2],
and
[Bi{(o-Me2NCH2)C6H3CO2}{o-
Me2N(O)CH2C6H3}].[15] There are no reports of stable and/
or structurally characterized monoarylbismuth(V) complexes
of the form [BiArX4].
ꢀ
As is typical for a heavy metal, Bi S bonds are generally
Scheme 1. Synthetic routes to the bismuth(V) thiolates [BiPh(4-MTT)4]
1 and [BiPh(2-MMI)4] 2.
ꢀ
less labile and thermodynamically more stable than Bi O
bonds.[16] Thus, bismuth(III) thiolates are common stable
species and have a special relevance in biology and medi-
cine.[17] While both Hoppe and Whitmire[8d] and Sharutin
et al.[8a–c] have had some success in synthesizing triarylbis-
muth(V) phenoxides, there is no corresponding thiolate
Electrochemical analysis of these solids, supported by NMR
spectroscopy, ESI-MS, and FTIR spectroscopy, showed them
to be the monophenyl tetrathiolato bismuth complexes
[BiPh(4-MTT)4] 1 and [BiPh(2-MMI)4] 2, in which the
bismuth(III) center has undergone oxidation to BiV following
protolysis and substitution of two Ph ligands and concomitant
addition of two further thiolato ligands. Synthesis under
microwave conditions provided slightly higher yields of 1 and
2, and in a fraction of the time (seven minutes versus nine
hours). Full synthetic and analytical details are provided in
the Supporting Information.
[*] A. Luqman, Dr. V. L. Blair, Prof. A. M. Bond, Prof. P. C. Andrews
School of Chemistry, Monash University, Clayton
Melbourne, VIC 3800 (Australia)
E-mail: phil.andrews@monash.edu
[**] We thank Monash University and the Australian Research Council
for financial support. A.L. thanks the Pakistan Government for the
award of an International Research Support Initiative Program
(IRSIP) Scholarship.
1
From integration of the proton signals in the H NMR
spectrum of both 1 and 2 the L/Ph ratio was calculated as 4:1.
There were no residual resonances attributable to NH, which
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/anie.201301200.
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are found at d = 13.7 and 12.0 ppm in MTT(H) and MMI(H),
respectively (or to SH because the thiones are stable to
tautomerization in DMSO solution at RT). In complex 1, the
signal at d = 8.27 ppm (8.43 in MTT(H)) can be assigned to
the proton on the triazole ring, while the two doublets at d =
6.80 and 6.96 ppm in 2 correspond to the protons on the
imidazole ring (d = 6.85 and 7.03 ppm in MMI(H)). The
phenyl protons in
1 resonated at 8.36 (o), 7.47 (m),
7.29 (p) ppm, while the corresponding signals in 2 were
observed at d = 8.83 (o), 7.49 (m), and 7.23 (p) ppm.
FTIR spectroscopy of both complexes supports the NMR
ꢀ
spectroscopic data. Absorption bands for N H (observed at
3115 and 3097 cmꢀ1 in MTT(H) and MMI(H), respectively),
ꢀ
or for S H bands (not observed in MTT(H) and MMI(H)),
Figure 1. 1H NMR spectral comparison of [BiPh(2-MMI)4] 2 and [BiPh-
(2-MMI)2{2-MMI(H)}2] 4.
were absent in the spectra obtained for complexes 1 and 2.
Further evidence for the formation of the two new hyper-
valent bismuth(V) complexes came from electrospray mass
spectrometry, for which the solid samples were dissolved in
DMSO/methanol. Complex 1 showed prominent peaks at
m/z 553.02 (33%, [BiPh(O)L2Na]+), 628.05 (81%,
[BiPhL3]+), and 765.05 (46%, [BiPhL4 + Na]+), while for 2
peaks were observed at 529.05 (8%, [BiPh(O)L2 + H]+),
625.07 (12%, [BiPhL3]+), 839.13 (58%, [BiPhL4(DMSO) +
Na]+), 875.11 (70%, [BiPhL4(DMSO)(H2O) + Na]+), and
911.09 (65%, [BiPhL4(DMSO)(H2O)4 + Na]+).
To gain some insight into the structure of both complexes,
crystals suitable for X-ray crystallography were obtained from
separate DMSO solutions of 1 and 2 after several months.
However, the X-ray diffraction data revealed them to be the
BiIII complexes [BiPh(4-MTT)2{4-MTT(H)}2] 3 and [BiPh(2-
MMI)2{2-MMI(H)}2] 4 rather than the anticipated BiV com-
plexes, which indicated that protonation of two thiolato
ligands had occurred accompanied by reduction of the BiV
center. Presumably this redox process resulted from the
presence of water in the DMSO during crystallization. In dry
DMSO under a dry nitrogen atmosphere, no crystallization
was observed after two months. Solution 1H NMR studies on
the crystals of 3, which are poorly soluble even in DMSO,
showed the NH protons resonating at d = 13.60 ppm, the
triazole CH proton shifted to d = 8.35 ppm (8.27 ppm in 1),
and the o-Ph signal now at 8.27 ppm (8.36 ppm in 1). These
C-H chemical shifts, including those for m- and p-Ph, are
identical to those found in the deliberately prepared BiIII
analogue [PhBi(4-MTT)2] (see below). The NH proton in the
spectrum of 4 was found at d = 12.00 ppm, and the signals for
the imidazole CH protons were found at d = 6.81 and
7.00 ppm (compared with 6.80 and 6.93 ppm in 2), shown in
Figure 1.
Figure 2. Molecular structure of [BiPh(4-MTT)2{4-MTT(H)}2] 3. Only
one of two independent molecules is shown; thermal ellipsoids at
50% probability. Hydrogen atoms (except N-H ones) have been
omitted for clarity. Selected bond lengths (ꢀ) and angles (8): Bi(1)-S(1)
2.8236(11), Bi(1)-S(2) 2.8055(11), Bi(1)-C(1) 2.204(5), S(1)-C(5)
1.725(4), S(2)-C(8) 1.715(4), N(1)-H(1) 0.880, H(1)-N(4)’ 1.861, Bi(1)-
S(1)-C(5) 90.05(15), Bi(1)-S(2)-C(8) 96.68(15), C(1)-Bi(1)-S(1)
91.42(2), C(1)-Bi(1)-S(2) 84.32(2), S(1)-Bi(1)-S(2) 88.20(4), S(1)-Bi(1)-
S(1)’ 177.17(4), S(2)-Bi(1)-S(2)’ 168.64(5), S(1)-Bi(1)-S(2)’ 92.08(4).
Complexes 3 and 4 contain a C2 axis along C(4), C(1),
Bi(1) and C(12), C(9) and Bi(1), respectively, and adopt
a distorted square-pyramidal geometry. The centrally located
BiIII atom is coordinated to one phenyl, two 4-MMT and two
MTT(H) ligands (3), or two 2-MMI and two 2-MMI(H)
ligands (4), giving each BiIII center a total coordination
number of five. The two hydrogen atoms H(1) and H(2N)
located on the neutral 4-MTT(H) and 2-MMI(H) ligands in 3
and 4, respectively, were located by residual density in the
electron difference maps and placed in the calculated
positions. Interestingly, with an overall C4v symmetry the
two complexes resemble the unusual structural motif only
observed with [BiAr5] complexes, which provides insight into
their BiV origin.
In the realm of bismuth(III) thiolate chemistry, complexes
3 and 4 (Figure 2 and Figure 3 respectively) are rare examples
of crystallographically characterized homometallic complexes
containing a triazole-thiolate or imidazole-thiolate ligand
system. The only other related examples are based on
substituted imidazole-thione ligands which are bound
datively to the BiIII center.[19–22] This indicates that when
deprotonated, the stable thione form converts to the more
stable thiolate anion upon bonding with bismuth, providing
ꢀ
a thermodynamically stable and non-labile Bi S bond.
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Figure 3. Molecular structure of [BiPh(2-MMI)2{2-MMI(H)}2] 4 show-
ing thermal ellipsoids at 30% probability. Hydrogen atoms (except N-
H ones) have been omitted for clarity. Selected bond lengths (ꢀ) and
angles (8): Bi(1)-S(1) 2.8112(10), Bi(1)-S(2) 2.8132(14), Bi(1)-C(9)
2.235(5), S(1)-C(1) 1.717(4), S(2)-C(5) 1.719(4), N(2)-H(2N) 0.880,
H(2N)···N(4) 1.848, Bi(1)-S(1)-C(1) 91.04(12), B(1)-S(2)-C(5)
95.92(12), C(9)-Bi(1)-S(1) 88.303(19), C(9)-Bi(1)-S(2) 87.67(2), S(1)-
Bi(1)-S(2) 91.84(4), S(1)-Bi(1)-S(1)’ 176.61(4), S(2)-Bi(1)-S(2)’
175.33(4), S(1)-Bi(1)-S(2)’ 88.03(4).
ꢀ
The Bi S bond lengths in complexes 3 and 4 are
essentially identical ranging from 2.8055(11)–2.8236(11) ꢀ,
showing little variation for the covalent versus dative
(coordinative) bonding modes. Thus, they constitute an
ꢀ
average between typical covalent Bi S (approximately
!
2.6 ꢀ),[23] and coordinate dative Bi
S
(approximately
3.0 ꢀ) bonds.[23d] This most likely arises from an averaging
of the four bonds throughout the crystal owing to the
possibility of the two calculated NH protons on the neutral
ligands being located on any two of the heterocyclic ligands at
any one time.
Figure 4. a) Two-step reduction of BiV in [BiPh(4-MTT)4] 1 to Bi0 under
In complex 3, bismuth and three of the sulphur atoms are
co-planar to within ꢁ 0.03 ꢀ with the S(2) atom lying out of
this plane by 0.624(3) ꢀ. In contrast the BiS4 equatorial
grouping in complex 4 is essentially co-planar (ꢁ 0.04 ꢀ).
Perpendicular to this BiS4 basal plane, the triazole-thione
ligand in 3 and the imidazole-thione ligand in 4 make
conditions of steady-state voltammetry at a carbon microelectrode;
b–d) cyclic voltammetry at a glassy carbon electrode; b) potential
switched after process A for complex 1; c) potential switched after
process B for complex 1; d) potential switched after process D giving
rise to reduction of BiIII in [BiPh(4-MTT)2{4-MTT(H)}2] 3 to Bi0.
a
hydrogen-bond contact to their symmetry-generated
acceptors (1.861 ꢀ, 3 and 1.848 ꢀ, 4) which lie almost co-
planar, twisted by 7.76(22)8 in 3 and 8.67(22)8 in 4. The Bi-S-C
angles in both complexes 3 (Bi(1)-S(1)-C(5) 90.05(15)8, Bi(1)-
S(2)-C(8), 96.98(15)8) and 4 (Bi(1)-S(1)-C(1), 91.04(12)8,
Bi(1)-S(2)-C(5), 95.92(12)8) are obtuse in nature and far
removed from the expected bond angle of around 1098 seen in
other similar Bi-S-C bonded complexes.[24]
In principle, voltammetric techniques can be used to
distinguish the redox level of inorganic compounds. Typically,
a BiV compound is expected to be reduced to the elemental
Bi0 state in two steps, when the potential is scanned in the
negative direction. That is, BiV is reduced to BiIII in a two-
electron step followed by a further three-electron step in
which BiIII is reduced to elemental Bi0. Subsequently,
elemental Bi0 deposited on the electron surface can be
stripped from the surface to give BiIII, by scanning the
potential in the positive direction. Figure 4a shows a steady
state voltammogram at a microelectrode for the reduction of
the presumed BiV compound in dry DMSO under a N2
atmosphere. The initial reduction step (process A) is well
defined. Upon scanning more negative potentials, a second
more drawn out reduction process is detected (process B).
The ratio of the limiting current for processes A and B is 2:3.
Thus, processes A and B are assigned to the reactions in
Equations (1) and (2), respectively.
BiV þ 2 eꢀ ! BiIII
ð1Þ
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BiIII þ 3 eꢀ ! Bi0
ð2Þ
reflux conditions in ethanol. Thermally induced homolytic
decomposition of the disulfide into two radical species[26]
would then allow formation of the BiV complex through Bi
ꢀ
Under transient conditions of cyclic voltammetry, proc-
ess A is still well defined [Figure 4b]. However, no bismuth
metal (here Bi0) is produced, as evidenced by the lack of
a bismuth stripping (Bi0!BiIII) process at positive potentials
on the reverse positive potential direction scan. In contrast, if
the potential is switched at a value more negative than
process B [Figure 4c], upon reversing the potential scan
direction, the characteristic bismuth-stripping peak is now
detected (process C). Furthermore, upon holding the poten-
tial at values between the first and second reduction process
for ten minutes, no elemental Bi0 was detected. However, if
the potential is held at a value slightly more negative than
process B, then upon removal of the working electrode from
the solution, a deposit can be visually detected on the glassy
carbon electrode. The XRD spectrum, provided in the
Supporting Information, confirmed that elemental bismuth
was deposited onto the electrode surface.
S bond formation, using the two available electrons on the
BiIII center, nominally the lone-pair electrons. To probe the
validity of this mechanism, BiPhL2 (L = 4-MTT(H)) was
synthesized by treating BiPhCl2 with two equivalents of [4-
MMINa]. The yellow solid product was washed with water
and ethanol and the composition confirmed through NMR
spectroscopy and elemental analysis (see Supporting Infor-
mation). The disulphide, 1,2-bis(4-methyl-4H-1,2,4-triazol-3-
yl)disulfane (L-L), derived from 4-MTT(H) was also pre-
pared.[27] Finally, BiPhL2 and L-L were dissolved in toluene in
a 1:1 ratio and heated under refluxing conditions for six hours
under a nitrogen atmosphere. The yellow product obtained
was washed with diethyl ether and shown to be complex 1,
[BiPh(4-MTT)4]. The radical nature of this oxidation process
is being probed further as we seek to determine the generality
of this reaction in forming novel BiV thiolato species.
Voltammetry of the compound tentatively assigned as
a BiIII material was significantly different to that described
above for the nominally BiV compound [Figure 4c]. In this
case, the initial process D is more drawn out than process A
but leads directly to detection of elemental bismuth (pro-
cess C) when the potential is reversed, as shown in Figure 4d.
Thus, process D can be assigned to the reaction BiIII + 3eꢀ!
Bi0. Other processes detected for the BiV and BiIII compounds
at very negative and positive potentials (data not shown) were
attributed to ligand reduction and oxidation, respectively. The
voltammetric data therefore lend support to the redox level
assignments given to the Bi compounds on the basis of NMR
and other data.
The voltammetric features of complexes 2 and 4 mimic
those of complexes 1 and 3. Thus, Bi metal is produced after
two steps with steady-state limiting currents in the ratio of 2:3
(Supporting Information, Figure S10) for complex 2, whereas
Bi metal is produced from the first step for complex 4
(Figure S13).
Received: February 11, 2013
Revised: March 8, 2013
Published online: June 6, 2013
Keywords: bismuth · electrochemistry · oxidation ·
.
structure elucidation · thiols
[1] A. J. Bard, R. Parsons, J. Jordan, Standard Potentials in Aqueous
Solutions, IUPAC (Marcel Dekker), New York, USA, 1985.
[2] C. Silvestru, H. J. Breunig, H. Althaus, Chem. Rev. 1999, 99,
3277.
[3] For example; a) S. Wallenhauer, D. Leopold, K. Seppelt, Inorg.
Chem. 1993, 32, 3948; b) A. Schmuck, J. Buschmann, J. Fuchs, K.
Seppelt, Angew. Chem. 1987, 99, 1206; Angew. Chem. Int. Ed.
Engl. 1987, 26, 1180; c) A. Schmuck, D. Leopold, S. Wallan-
hauer, K. Seppelt, Chem. Ber. 1990, 123, 761.
[4] a) C. C. Caires, S. Guccione, Organometallics 2008, 27, 747; b) T.
Murafuji, T. Azuma, Y. Miyoshi, M. Ishibashi, A. F. M. M.
Rahman, K. Migita, Y. Sugihara, Y. Mikita, Bioorg. Med. Chem.
Lett. 2006, 16, 1510; c) Y. Kang, D. Song, H. Schmider, S. Wang,
Organometallics 2002, 21, 2413; d) S. Yamaguchi, T. Shirisaka, K.
Tamao, Organometallics 2002, 21, 2555.
[5] a) Y. Matano, H. Nomura, J. Am. Chem. Soc. 2001, 123, 6443;
b) V. V. Sharutin, I. V. Egorova, O. K. Sharutina, T. K. Ivanenko,
I. I. Pavlushkina, A. V. Gerasimenko, M. A. Pushilin, Russ. J.
Gen. Chem. 2004, 74, 1466.
Having established definitively that the BiV complexes
were formed in the reaction of BiPh3 with the N-heterocyclic
thiols the question remained as to how this oxidation of the
BiIII species occurs. A recent paper by John and co-workers
suggests a possible mechanism,[25] illustrated for our systems
in Scheme 2. Here the thiol converts to the disulfide under
[6] a) I. V. Egorova, V. V. Sharutin, T. K. Ivanenko, N. A. Niko-
laeva, A. A. Molokov, G. K. Fukin, Koord. Khim. 2006, 32, 672;
b) G.-C. Wang, J. Xiao, Y.-N. Lu, L. Yu, H.-B. Song, J.-S. Li, J.-R.
Cui, R.-Q. Wang, F.-X. Ran, H.-G. Wang, Appl. Organomet.
Chem. 2005, 19, 113; c) L. Yu, Y.-Q. Ma, G.-C. Wang, J.-S. Li, G.-
H. Du, J.-J. Hu, J. Organomet. Chem. 2003, 679, 173; d) A.
Miloudi, G. Boyer, D. El-Abed, J.-P. Finet, J.-P. Galy, Main
Group Met. Chem. 2001, 24, 767.
[7] a) V. V. Sharutin, I. V. Egorova, A. P. Pakusina, O. K. Sharutina,
M. A. Pushilin, Koord. Khim. 2007, 33, 168; b) V. V. Sharutin,
I. V. Egorova, T. K. Ivanenko, O. K. Sharutina, D. Y. Popov,
Koord. Khim. 2003, 29, 502.
[8] a) V. V. Sharutin, I. V. Egorova, O. K. Sharutina, A. P. Pakusina,
M. A. Pushilin, Koord. Khim. 2007, 33, 12; b) V. V. Sharutin, I. V.
Egorova, T. V. Tsiplukhina, A. A. Molokov, G. K. Fukin, Russ. J.
Gen. Chem. 2005, 75, 927; c) V. V. Sharutin, I. V. Egorova, T. V.
Tsiplukhina, T. K. Ivanenko, M. A. Pushilin, A. V. Gerasimenko,
Scheme 2. Mechanistic reaction pathway where L=4-MTT or 2-MMI.
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Russ. J. Inorg. Chem. 2004, 49, 1475; d) S. Hoppe, K. H.
Whitmire, Organometallics 1998, 17, 1347.
[9] V. V. Sharutin, I. V. Egorova, T. K. Ivanenko, A. V. Gerasi-
menko, Koord. Khim. 2003, 29, 163.
[10] S. Marriott, W. F. Reynolds, R. W. Taft, R. D. Topsom, J. Org.
Chem. 1984, 49, 959.
[20] D. J. Williams, J. T. Anderton, E. A. Armstrong, M. H. Bowen,
R. E. Hart, S. K. Tata, D. R. Smith, K. M. White, D. Vanderveer,
Main Group Chem. 2007, 6, 263.
[21] D. J. Williams, A. M. Hutchings, N. E. McConnell, R. A.
Faucher, B. E. Huck, C. A. S. Brevett, D. Vanderveer, Inorg.
Chim. Acta 2006, 359, 2252.
[11] a) S. Wallenhauer, K. Seppelt, Angew. Chem. 1994, 106, 1044;
Angew. Chem. Int. Ed. Engl. 1994, 33, 976; b) B. Neumꢁller, K.
Dehnicke, Chem. Int. Ed. Engl. 1994, 33, 1726.
[12] Y. Matano, Bismuth-Mediated Organic Reactions, Topics in
Current Chemistry 311, Springer, Berlin, 2012, Chap. 2.
[13] Y. Matano, H. Nomura, H. Hisanaga, H. Nakano, M. Shiro, H.
Imahori, Organometallics 2004, 23, 5471.
[22] D. J. Williams, T. Carter, K. L. Fahn, D Vanderveer, Inorg. Chim.
Acta 1995, 228, 69.
ꢀ
[23] For some examples of common Bi S bond lengths see: a) H.
Sommer, A. Eichhofer, D. Fenske, Z. Anorg. Allg. Chem. 2008,
634, 436; b) D. A. Atwood, A. H. Cowley, R. D. Hernandez,
R. A. Jones, L. L. Rand, S. G. Bolt, J. L. Atwood, Inorg. Chem.
1993, 32, 2972; c) D. S. Sagatys, G. Smith, R. C. Bolt, P. C. Healy,
Aust. J. Chem. 2003, 56, 941; d) H. Suzuki, Y. Matano, Organo-
bismuth Chemistry, Elsevier, Amsterdam, 2001, Chap. 2, p. 133.
[14] A. P. Soran, M. G. Nema, H. J. Breunig, C. Silvestru, Acta
Crystallogr. Sect. E 2011, 67, m153.
ꢀ ꢀ
[15] L. Balazs, H. J. Breunig, E. Lork, A. Soran, C. Silvestru, Inorg.
Chem. 2006, 45, 2341.
[16] N. C. Norman, Chemistry of Arsenic, Antimony and Bismuth,
Thomson Science, London, 1998.
[17] a) The Biological Chemistry of Arsenic Antimony and Bismuth
(Ed.: H. Sun), Wiley, London, 2011; b) R. Ge, H. Sun, Acc.
Chem. Res. 2007, 40, 267; c) P. J. Sadler, H. Li, H. Sun, Coord.
Chem. Rev. 1999, 185 – 186, 689.
[18] M. M. Khodaei, I. Mohammadpoor, K. Nikoofar, Bull. Korean
Chem. Soc. 2003, 24, 885.
[24] For some examples of Bi S C common bond angles see: a) J. X.
Chen, X. Y. Tang, Z. G. Ren, Y. Zhang, J. P. Lang, Eur. J. Inorg.
Chem. 2009, 38; b) M. Bao, T. Hayashi, S. Shimada, Dalton
Trans. 2004, 2055; c) J. P. H. Charmant, A. H. M. M. Jahan, N. C.
Norman, A. G. Orpen, Inorg. Chim. Acta 2005, 358, 1358.
[25] P. Kalimuthu, P. Kalimuthu, S. A. John, Nature Precedings, 2007,
http://hdl.handle.net/10101/npre.2007.734.1.
[26] P. Huston, J. H. Espenson, A. Bakac, J. Am. Chem. Soc. 1992,
114, 9510.
[27] B. Zeynizadeh, J. Chem. Res. 2002, 564.
[19] D. J. Williams, B. Rubin, J. Epstein, W. K. Dean, A. Vienbeck,
Cryst. Struct. Commun. 1982, 11, 1.
Angew. Chem. Int. Ed. 2013, 52, 7247 –7251
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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