Anionic Bismuth(III) chloride cluster with diselenide countercations: Application in C-S cross coupling reactions

Article abstract of DOI:10.1016/j.jorganchem.2019.01.017

The first weakly coordinating anion (WCA) with reactive p-block cation (rPBC) type of [(Bi₄Cl₁₆)^4-{(LSeSeL)²⁺}₂], L = 1,3-bis(2-benzhydryl-4,6-dimethylphenyl)-1H-imidazole-2(3H), ion pair is reported. The tetranuclear anionic bismuth(III) cluster shows a new type of ladder structure with two different types of Bi(III) coordination modes. In the solid state structure, the tetranuclear bismuth(III) cluster is sandwiched by two diselenide cations through hydrogen bonding interactions. Besides, this ion pair has been efficaciously employed as catalyst in C-S cross-coupling reactions under optimized reaction condition. This ion pair depicted a wide range of substrate scope with different thiols and aryl halides.

Full text of DOI:10.1016/j.jorganchem.2019.01.017

Accepted Manuscript
Anionic Bismuth(III) chloride cluster with diselenide countercations: Application in C-S
cross coupling reactions
Ganesan Prabusankar, Mannem Adinarayana, Muthukumaran Nirmala
PII:
S0022-328X(18)31005-2
DOI:
https://doi.org/10.1016/j.jorganchem.2019.01.017
JOM 20695
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 28 November 2018
Revised Date: 17 January 2019
Accepted Date: 23 January 2019
Please cite this article as: G. Prabusankar, M. Adinarayana, M. Nirmala, Anionic Bismuth(III) chloride
cluster with diselenide countercations: Application in C-S cross coupling reactions, Journal of
Organometallic Chemistry (2019), doi: https://doi.org/10.1016/j.jorganchem.2019.01.017.
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Graphical abstract
The diselenide trapped tetranuclear anionic bismuth(III) chloride cluster for C-S cross-coupling
reaction is reported.

ACCEPTED MANUSCRIPT
Anionic Bismuth(III) Chloride Cluster with Diselenide Countercations:
Application in C-S Cross Coupling Reactions
Ganesan Prabusankar,* Mannem Adinarayana and Muthukumaran Nirmala
a
Department of Chemistry, Indian Institute of Technology Hyderabad, Kandi, Telangana, INDIA.
5
02 285 Fax: +91 40 2301 6032; Tel: +91 40 23016089; E-mail: prabu@iith.ac.in
Abstract
The first weakly coordinating anion (WCA) with reactive p-block cation (rPBC) type of
4
-
2+
[
(Bi Cl ) {(LSeSeL) } ], L = 1,3-bis(2-benzhydryl-4,6-dimethylphenyl)-1H-imidazole-2(3H),
4 16 2
ion pair is reported. The tetranuclear anionic bismuth(III) cluster shows a new type of ladder
structure with two different types of Bi(III) coordination modes. In the solid state structure, the
tetranuclear bismuth(III) cluster is sandwiched by two diselenide cations through hydrogen
bonding interactions. Besides, this ion pair has been efficaciously employed as catalyst in C-S
cross-coupling reactions under optimized reaction condition. This ion pair depicted a wide range
of substrate scope with different thiols and aryl halides.
Keywords: Bismuth, Selone, Ion pair, C-S cross-coupling
1

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1
. Introduction
The N-heterocyclic carbene (NHC) analogues of chalcogenones (S, Se, Te), have
depicted the upsurge growth in the field of organometallic chemistry owing to their potential
applications in supramolecular, [1] medicinal [2] and materials chemistry [3-6]. Especially, the
oxidation of imidazole selone is known as the pivotal reaction in the metabolism of several
biological process [7]. Such oxidation of 1,3-disubstituted imidazole was carried out under
suitable conditions using suitable oxidizing agents such as 7,7’,8,8’-tetracyano-p-
2 2
quinodimethane [8] or I [9,10] or Te or ICl or IBr [8,11] or Br [12–14] or HCl/air [15–17].
Several 1,3- disubstituted imidazole diselenide dications have been isolated and most of them are
structurally characterized [18]. However, the metal catalysed oxidation of 1,3-disubstituted
imidazole selone or thione has not been realized until 2011 [19]. The first triflate salts of 1,3-
disubstituted imidazole disulfide dications or diselenide dications have been derived using
Cu(OTf)
(HCN(C H -iPr -2,6)) C}; IPr’ = [(HC) {N(C H -iPr -2,6)}{NCH C(O)OMe}C}] by Bi(OTf)
3
2
[20]. Later, the oxidative reaction of sterically crowded IPrSe or IPr’Se (IPr =
{
6
3
2
2
2
6
3
2
2
2
+ -
2+
or Cu(-ClO ) ·6H O was reported to isolate [(IPr)Se] { OTf} ] or [(IPr‘)Se] {-O Cl} ],
4
2
2
2
2
2
4
2
respectively [21]. Although the metal salt route to imidazole diselenide dication is well
established, the weakly coordinating anion (WCA) with reactive p-block cations (rPBC) class of
pair is not known [22].
Thus, we now report the isolation of first bismuth tetra anionic salt as WCA with semi-
super bulky bis-1,3-diimidazole diselenide as rPBC from the direct oxidation of 1,3-bis(2-
benzhydryl-4,6-dimethylphenyl)-1H-imidazole-2(3H)-selenone (1) by BiCl
3
. In addition, the
application of WCA-rPBC pair in C-S cross coupling reactions are demonstrated.
2
. Results and discussion
2
.1. Synthesis and characterization of 1 and 2
Organo imidazolin-2-selone ligand 1 with spatially defined steric impact was synthesized
in very good yield from the reaction between 1,3-bis(2-diphenylmethyl-4,6-dimethylphenyl)-
imidazolium chloride and elemental selenium powder in the presence of activated K CO in
2
3
methanol (Scheme 1) [23]. In solution state, 1 adopts two different conformations with 2:1 ratio.
The mixture of two conformations was obtained in deuterated chloroform solution. However, the
2

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1
13
identity of each rotamer was very complicated. In NMR analysis, H and C spectra gave
complicated splitting and related information due to free rotation around C-N bond slowing the
interchange between conformations. The rotamers of the ligand was confirmed by FT-IR,
1
13
multinuclear ( H and C) NMR, and TGA. In molecule 1, the FTIR stretching frequency for
-1
1
C=Se was located at 1266 and 1167 cm . Upon seleniation, the H NMR signal for the acidic
N(CH)N protons (around δ = 10.5-12.0) present in 1,3-bis(2-benzhydryl-4,6-dimethylphenyl)-
1
3
1
H-imidazolium chloride was absent in imidazolin-2-selone (1). In C NMR, the carbene carbon
attached to selenium shows two signals at δ = 159.1 and 158.1.
Scheme 1. Synthesis of 1.
Subsequently, the tetra nuclear bismuth(III) selone complex 2 was synthesized from the
reaction between BiCl , and an equimolar quantity of organo selone (1) in toluene at room
3
temperature (Scheme 2). The complex 2 was isolated as orange red precipitate with good yield. 2
is soluble in highly polar organic solvents like methanol, acetonitrile and dimethyl sulfoxide,
while insoluble in dichloromethane, chloroform and petroleum ether. 2 is stable under ambient
1
condition. The H NMR chemical shift values of 2 are almost similar to that of 1.
3

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Scheme 2. Synthesis of 2.
1
3
The C NMR chemical shift value of C=Se in 2 showed δ 1-3 upfield shift compared to
that of 1. The solid state structure of 2 was further confirmed by single crystal X-ray diffraction
technique. The suitable single crystals for the X-ray analysis of 2 were isolated from the
saturated solutions of acetonitrile at room temperature (Table 4). The X-ray crystallographic
4

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analyses of 2 suggests that the syn conformer is preferred in the solid state due to intermolecular
interactions [23].
Figure 1. Molecular structure of 2. Hydrogen atoms are omitted for clarity. Selected bond
o
lengths (Å) and bond angles ( ): C(1)–Se(1), 1.894(8), Se(1)–Se(2) 2.345(12), Bi(1)–Cl(7)
2
2
9
8
.489(3), Bi(1)–Cl(6) 2.545(2), Bi(1)–Cl(8) 2.542(2), Bi(2)–Cl(2) 2.527(3), Bi(2)–Cl(3)
.685(2), Bi(2)–Cl(4) 2.557(2), Bi(2)–Cl(5) 2.747(2), Bi(2)–Cl(1) 2.927(2), Cl(6)–Bi(1)–Cl(8)
2.33(7), Cl(6)–Bi(1)–Cl(7) 93.74(10), Cl(3)–Bi(2)–Cl(5) 174.53(8), Cl(1)–Bi(2)–Cl(5)
4.23(7), Cl(2)–Bi(2)–Cl(5) 90.25(9), N(1)–C(1)–N(2) 107.1(7), N(1)–C(1)–Se(1) 122.22(6).
C(1)–Se(1)–Se(2) 99.1(3).
2
is a rare example for the weakly coordinating anion (WCA) with reactive p-block
cations (rPBC) class of pair. The tetra anionic tetranuclear bismuth(III) chloride cluster,
4
-
4-
[
Bi Cl ] is stabilized by the two diselenide counter cations (Figure 1). Interestingly, [Bi Cl ]
2
1
6
2
1
6
in 2 shows an unusual structural motive with two different types of coordination environment
around bismuth(III) centers.
5

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4
-
Scheme 3. Possible mechanism for the formation of [Bi Cl ] .
4
16
4
-
The possible mechanism for the formation of [Bi
4
Cl16] can be rationalized through the
2
-
-
formation of edge-edge dimer [Bi Cl ] from Ψ-square-based pyramidal [BiCl ] unit with
2
8
4
2
-
retention of lone-pair electrons (Scheme 3) [44a]. Further dimerization of [Bi
2
Cl
8
] anions could
4
-
lead to the formation of [Bi Cl ] anions, which got trapped by two semi-super bulky diselenide
4
16
4
-
cations. Though few [Bi Cl ] clusters have been reported with cations like [Mg(MeCN) ]
6 2
4
16
[24a], N,N,N’,N’,N’’,N’’-hexamethylguanidinium ion [24b], 1-butylpyridinium cation [24c],
and (Ph P) [24d], in all these cases Bi(III) centers are in a distorted octahedral geometry with six
4
4
chloride ions (Type A cluster, Scheme 3). The major structural difference between the known
4
-
4-
2
[
Bi Cl ] cluster vs present [Bi Cl ] cluster is that the lack of two µ bridging chloride ions in
4 16 4 16
4
-
2
to result a new type of [Bi Cl ] structural motif with lone pair elections (Type B cluster,
4 16
Scheme 3). The distance between Bi(1) and Cl(3)/Cl(4) is 3.008 Å, which is slightly far from the
4
-
Bi‒Cl bond distance found in 2. Thus, [Bi Cl ] ion in 2 is in ladder structure and this can be
2
16
2
3
3
3 3 2
considered as dimerized [Cl Bi(µ Cl)(µ Cl)BiCl ] through µ bridging chloride ligands. The
geometry of each Bi(1) center is penta coordinated by three terminals, one doubly bridged and
6

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one triply bridged chloride ions. The geometry of Bi(1) can be described as square pyramidal
geometry. The Bi(2) center in 2 is fulfilled by three terminal, two doubly bridged and one triply
bridged chloride ions. The geometry of Bi(2) can be considered as octahedral. The diselenide
fragment Se‒Se is connected by two semi bulky imidazole ligands. The terminal Bi–Cl bond
distances around Bi(1) and Bi(2) are not comparable. The Bi(1)–Cl(7) depicts the shortest bond
distance while Bi(2)–Cl(1) shows the longest bond distance. The terminal Bi–Cl bond lengths are
shorter than the bridging Bi–Cl bond distances. The Se‒Se bond lengths in 2 is 2.345(12) Å,
2
+
–
which is slightly shorter than the presciently reported [{(HCN(Me)) CSe} ] [{ OTf} ] 2.360(7)
2
2
2
2
+
+
Å [25], [{(HCN(Me))
2
CSe}
2
] {I}
2
] (2.434(2) Å), [{(HCN(Me))
2
CSe}
2
Cl] {I
3
¯ }] (2.440(2) Å)
[
26] and [ IPrSe(OTf) ] 2.427(5) Å [21]. The C–Se bond lengths in 2 is comparable and slightly
2 2
shorter than IPr*Se (1.942(16) Å) [27]. As shown in figure 2, the WCA and rPBC are held
….
.....
together through C–H Cl (2.727(1) and 2.837(1) Å) and Se N (2.782(1)-2.849(1) Å) hydrogen
4
-
bonding interactions. The WCA, [Bi Cl ] is sandwiched by two rPBC diselenides (Figure 3).
2
16
….
....
Figure 2. The C-H Cl and Se N bonding interactions between WCA and rPBC in 2.
7

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Figure 3. Space filling modal of 2.
Thermogravimetric analysis
Stability of 2 was accomplished by thermal gravimetric analysis (TGA) and compared
o
o
with 1 (Figure 4). 1 depicted a clear two stage weight losses from 290 C to 440 C with 79%
o
o
weight loss then 21% weight loss from 440 C to 620 C, which can be attributed to the
decomposition of organic moieties followed by selenium. The molecule 2 showed considerable
o
o
stability till 290 C then gradual weight loss till 770 C with 84% weight loss due to the
decomposition of organic moieties. The remaining 16% residue can be attributed to the Bi Se
2
3
material.
8

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Figure 4. TGA curves of 1 and 2 from 35 °C to 800 °C recorded with heating rate of 10 °C
−
1
min under nitrogen atmosphere.
2
2
.2 Catalysis
.2.1. C-S cross coupling reactions
Transition metal catalyzed cross-coupling reactions have found widespread popularity in
synthetic chemistry [23]. The C‒S bond plays an important role in numerous compounds for
biological and pharmaceutical applications as well as for the precursor based materials chemistry
[29–39]. The traditional methods for C‒S bond formation often employs the harsh conditions.
For example, the coupling of thiolates with aryl halides takes place in hexamethylphosphoramide
at 200 ºC. The reduction of sulfoxide/sulfone is carried out with strong reducing agents like
DIBAL-H and LiAlH [40, 41]. To overcome such drawbacks, considerable research on the
4
development of catalytic systems for the C‒S cross-coupling of thiols with aryl halides have
been developed. In 1978, Migita and co-workers reported the first C–S cross-coupling of aryl
halides with thiols using tetrakis(triphenylphosphine)-palladium as catalyst [30]. Later, several
metal catalysts in which palladium [31], nickel [32], cobalt [33], copper [34], rhodium [35],
indium [36], zinc [37] and bismuth [42] serve as the metal sources in combination with
appropriate ligands have been developed. Out of these metals, the main group bismuth is more
attractive over other metals owing to its benign nature. Of-late, the applications of bismuth
compounds in organic transformations have been extensively investigated [43, 44]. Notably, the
9

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catalytic applications of bismuth selone compounds are very scarce in the literature. Recently,
we have demonstrated the first catalytic application of NHC‒Bi analogue of monoimidazoline-2-
chalcogenone derivatives of Bi(III) for O-acylative cleavage of cyclic ethers [45]. Subsequently,
the bismuth(III) dichalcogenones derivatives of triflates and halides were isolated and observed
to be highly active catalysts in synthesis of triaryl- or triheteroarylmethanes [46]. Based on the
above fact, the expansion of bismuth chemistry has aroused interest in recent years for various
organic transformations [43, 46, 47].
Scheme 4. 2 catalyzed C-S cross coupling reaction between 1-bromo-4-nitrobenzene and
thiophenol.
Thus, 2 was used as catalyst in C-S cross coupling reactions and explore the scope of the
catalyst. To optimize the reaction condition, the cross coupling reaction of 1-bromo-4-
nitrobenzene and thiophenol was chosen as a model reaction (Scheme 4). The effect of
catalyst loading and reaction time on C-S cross coupling reaction were investigated.
Thus, the reaction was performed with different catalytic amounts ranging from 2-12 mol
%
at different time intervals (Figure 5). The best conversion was obtained with 10 mol %
catalytic loading within 16 h. Besides, the effect of base and the choice of solvent for C-S
t
cross coupling reactions were examined using catalyst 2. After screening with KO Bu,
t
t
KOH, NaO Bu and K CO , NaO Bu was found to be the best base (Table 2). Among
2
3
toluene, 1,4-dioxane, MeCN and THF, MeCN seems to be best choice. Thus, it appears
that the C-S cross coupled product can be isolated in good yield from the reaction
t
between thiophenol and aryl halides in the presence of L-proline (10 mol%) and NaO Bu
(
2eq) in CH CN at 85 ºC.
3
1
0

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The cross coupling reaction between 1-bromo-4-nitrobenzene and thiophenol was
t
performed without catalyst 2 but in the presence of L-proline (10 mol %) and NaO Bu (2eq) in
CH CN at 85 ºC, which resulted in lower yield of the desired product (35%). Moreover, the
3
3
above cross coupling reaction under same condition but in a mixture of solvents CH CN and
H O (1:1), gave poor yield. The cross coupling reaction between 1-bromo-4-nitrobenzene and
2
t
thiophenol with catalyst BiCl
3
, L-proline (10 mol %) and NaO Bu (2eq) in CH
3
CN at 85 ºC gave
moderate conversion (42%).
Figure 5. Effect of catalyst mol % (2-12 mol%) with respect to time (4 –20 h) on C-S cross
coupling reaction between 1-bromo-4-nitrobenzene with thiophenol.
In order to expand the scope of the present protocol, the C-S cross coupling reactions
were performed with different thiols and aryl halides under optimized conditions (Table 3). The
reaction of 4-chlorothiophenol with 1-bromo-4-nitrobenzene and 1-bromo-2-nitrobenzene
afforded the corresponding (4-chlorophenyl)(2-nitrophenyl)sulfane and 4-chlorophenyl)(4-
nitrophenyl)sulfane in 89% and 80 % yield, respectively (Table 3, Entries 1 and 2). The reaction
of 4-chlorothiophenol with 4-bromobenzonitrile resulted the 4-((4-chlorophenyl)thio)benzonitrile
in very good yield (Table 3, Entry 4). Interestingly, the aryl halides with electron withdrawing
groups (Cl, Br and I) (Table 3, Entries 3, 4, 5 and 9) gave good yield than aryl halides with
electron donating substituents (Table 3, Entries 8 and 11). The coupling of mercaptobenzonitrile
1
1

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with 1-bromo-4-nitrobenzene gave the coupled product in 84 % yield (Table 3, Entry 6). The
coupling of 4-chlorobenzonitrile with benzene thiol underwent smoothly to provide the 4-
(phenylthio)benzonitrile product in 85 % yield (Table 3, Entry 10). Noteworthy that the isolated
yield under the present synthetic methodology is more convenient and more economic under
mild reaction conditions compared to the previous literature report [48]. The detailed mechanism
of the reaction is not clear at this stage as cited for most of the examples [23], however the
efforts are underway to explore the reaction mechanism.
3
. Conclusions
In conclusion, we have reported the synthesis and structural characterization of first rPBC
and WCA model of semi-super bulky bis-1,3-diimidazole diselenide and tetranuclear bismuth
anionic salt from the direct reaction of BiCl with the 1,3-bis(2-benzhydryl-4,6-dimethylphenyl)-
3
4
-
1
H-imidazole-2(3H)-selenone. The solid state structure of 2 reveals that WCA, [Bi Cl ] is held
2 16
….
.....
together by two rPBC diselenides through C–H Cl and Se N hydrogen bonding interactions.
4
-
Interestingly, [Bi Cl ] in 2 shows an unusual structural motive with two different types of
2
16
4
-
2
coordination environment around bismuth(III) centers. The [Bi Cl16] ion in 2 exist in ladder
structure. Subsequently 2 was successfully employed for the C-S cross coupling reaction of aryl
halides and thiols under acetonitrile medium. The present catalytic system best owed the C-S
cross coupling reactions with broad scope of thiols together with aryl halides. Indeed, the out-
come of the current work will significantly endow towards the exploration and growth of
bismuth chalcogenide chemistry for the synthesis of thioethers. Further explorations in this
direction are in progress.
4
. Experimental section
4
.1 General comments
The reactions were carried out in oven dried glassware with magnetic stirrer and without inert
gas protection. The commercial chemicals were used as purchased. 1 was prepared according to
the earlier proclaimed methods [23]. FT-IR measurement (neat) was carried out on a Bruker
Alpha-P Fourier transform spectrometer. Microanalyses of carbon, hydrogen and nitrogen were
1
2

ACCEPTED MANUSCRIPT
carried out using a Euro EA - CHNSO Elemental Analyzer. Thermogravimetric analysis (TGA)
was performed using a TASDT Q600, Tzero-press. NMR spectra were recorded on Bruker
o
Ultrashield-400 spectrometers at 25 C unless otherwise stated. Chemical shifts are given relative
to TMS and were referenced to the solvent resonances as internal standards. Single crystals of
complex suitable for the single crystal X-ray analysis were obtained from their reaction mixture
at room temperature and the suitable single crystals for X-ray structural analysis were mounted at
room temperature (150 K) in inert oil under an argon atmosphere. The crystal structure of 2 was
measured on an Oxford Xcalibur 2 diffractometer. Using Olex2 [49] the structure was solved
with the ShelXS [50] structure solution program using Direct Methods and refined with the
olex2.refine refinement package using Gauss-Newton minimization. Absorption corrections were
performed on the basis of multi-scans. Non-hydrogen atoms were anisotropically refined.
Hydrogen atoms were included in the refinement in calculated positions riding on their carrier
atoms. No restraint has been made for any of the compounds. 2 gave both “A” level and “B”
level alerts due to improper convergence of the refinement and variation in residual density.
Attempts to rectify these issues were not fruitful. CCDC 1881751 contains the supplementary
crystallographic data for this paper. These data can be obtained free of charge from the
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif or from the
Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44
1
223 336 033; or e-mail: deposit@ccdc.cam.ac.uk.
4
.2. Synthesis of 2
A mixture of 1 (100 mg, 1 mmol) and BiCl (65.19 mg, 1 mmol) in toluene (5 mL) was
3
stirred for 24 hours at room temperature to yield the pale red precipitate. The reaction mixture
was filtered, the precipitate was washed with hexane (2 x 5 mL) and then the precipitate was
dried and dissolved in acetonitrile to isolate the pale red crystals of 2. Yield 82% (based on
3 164 8 4 4
BiCl ). M.p.: 180-183 °C. CHN analysis for C180H N Se Cl16Bi (MW: 4158.29) (%): Calcd.
1
C, 51.99; H, 3.98; N, 2.69. Found C, 52.2; H, 4.1; N, 2.7. H NMR (400 MHz, CDCl ) δ: 7.34-
3
1
3

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7
2
.13 (20H, m, Ar-H), 6.89-6.76 (4H, m, Ar-H), 6.52-6.22 (2H, s, N(CH) N), 5.47-5.43 (2H, s,
1
3
CH(Ph ), 2.23 (6H, s, CH ), 1.99 (6H, s, CH ). C NMR (100 MHz, CDCl ) δ: 157.2, 156.3, (C-
2
3
3
3
Se), 143.4, 143.2, 141.8, 140.5, 134.7, 138.5, 137.3, 135.8, 135.6, 134.0, 129.7, 129.4,129.2,
-
1
2 3
28.8, 128.3, 128.1, 128.0126.4, 125.4, (CAr), 51.01, 50.9 (CHPh ), 20.9, 17.8 (CH ). FT-IR (cm
1
,
neat): 3020(bw), 2358(m), 1952(bw), 1694(m), 1597(m), 1547(m), 1483(s), 1341(bw),
1
243(m), 1159(m), 1078(m), 1032(m), 858(m), 739(s), 698(s), 628(m).
4
.3. General procedure for Bi(III)-selone catalyzed C-S cross coupling reactions
A mixture of thiophenol (1 mmol), aryl halide (1. 2 mmol), L–proline (10 mol%) and 2
o
(
10 mol%) in acetonitrile (5 mL) was stirred at 85 C. The reaction mixture was monitored by
TLC until all thiophenol was found consumed. The reaction mixture was extracted with ethyl
acetate and water, the organic layer was separated then washed with NaCl and dried with
anhydrous Na SO The solvent was removed under reduced pressure using the rotatory
2
4.
evaporator. The crude product was purified by column chromatography (5:95 of ethyl acetate
and hexane) to isolate the yellow solid.
Acknowledgements
GP gratefully acknowledge the DST-SERB (EMR/2017/001211) for financial support. MA
thank CSIR-JRF for the fellowship. MN thank DST-NPDF (PDF/2016/001834) for fellowship.
Appendix A. Supplementary data
1
13
Supplementary data ( H and C NMR spectra of the synthesized complex. Catalysis protocols
and characterization data of coupling products) related to this article can be found at. CCDC
1
881751. Single crystal X-ray data can be obtained free of charge from the Cambridge
Crystallographic Data center via www.ccdc.cam.ac.uk/data_request/cif.
5
. References
1
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4

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9

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Table 1.Crystallographic data, details of data collection and structure refinement parameters for
2
.
Parameters
2
Empirical formula
C
180 4 8 4
H160Bi Cl16N Se
Formula weight
Temperature (K)
4154
150
Crystal system
Triclinic
Space group
Pī
a/Å
b/Å
c/Å
α/°
β/°
15.1171(5)
15.3407(3)
19.2555(5)
76.864(2)
82.029(2)
87.196(2)
4305.9(2)
2
γ/°
3
Volume (Å )
Z
ρcalc/mg mm
Absorption coefficient (µ/mm )
F(000)
-3
1.6020
5.221
2023.1
-1
Reflections collected
90373
R
int
0.1080
1.044
0.0709
0.1913
2
GOF on F
(I>2ϭ(I))
wR (I>2ϭ(I))
R
1
2
R
1
values (all data)
0.0940
R2 values (all data)
0.2110
1

ACCEPTED MANUSCRIPT
Table 2. Effect of base and solvent on C-S cross coupling reaction of 1-bromo-4-nitrobenzene
a
with thiophenol
b
Entry
Base
KOtBu
NaOtBu
KOH
Solvent
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
THF
THF
THF
THF
Toluene
Toluene
Temp (ºC)
101
101
101
101
66
Yield (%)
48
1
2
3
4
5
6
7
8
9
65
51
65
62
51
50
62
41
48
89
75
67
29
56
69
K
2
CO
3
NaOtBu
KOtBu
KOH
66
66
66
110
110
85
85
85
K CO3
2
NaOtBu
KOH
NaOtBu
KOH
1
0
c
1
1
CH CN
3
1
1
2
3
CH CN
3
K CO3
CH CN
2
3
d
1
1
1
4
5
6
NaOtBu
NaOtBu
NaOtBu
CH CN
85
85
85
3
e
f
CH CN
3
CH CN
3
a
Reaction conditions: 1-bromo-4-nitrobenzene (1 mmol), thiophenol (1
t
mmol), NaO Bu (2 equiv.), L-proline (10 mol %), solvent (5 mL) and
catalyst (10 mol %) for 16 h.
b
Isolated yield after column chromatography.
Better optimization condition.
c
d
Reaction conditions: 1-bromo-4-nitrobenzene (1 mmol), thiophenol (1
t
mmol), NaO Bu (2 equiv.), L-proline (10 mol %) and solvent (5 mL) for
4
8 h (absence of catalyst).
e
Reaction conditions: 1-bromo-4-nitrobenzene (1 mmol), thiophenol (1
mmol), NaO Bu (2 equiv.), L-proline (10 mol %), solvent (5 mL) and
t
catalyst (5 mol %) for 24 h.
f
Reaction conditions: 1-bromo-4-nitrobenzene (1 mmol), thiophenol (1
t
mmol), NaO Bu (2 equiv.), L-proline (10 mol %), solvent (5 mL) and
catalyst (7 mol %) for 24 h.
2

ACCEPTED MANUSCRIPT
a
Table 3. C-S cross coupling of thiophenols with aryl halides catalyzed by 2.
b
S. No
Arylhalides
Thiols
Product
Yield (%)
b
1
89
2
80
c
3
76
83
89
d
4
5
3

ACCEPTED MANUSCRIPT
6
84
7
8
84
78
9
80
1
0
85
72
11
a
t
Reaction conditions: Aryl halides (1.2 mmol), thiophenols (1 mmol), NaO Bu (2 equiv.),
o
catalyst (10 mol %) and L-proline (10 mol %) in CH CN for 16 h at 85 C.
3
b
Entry number, isolated yield after column chromatography (%).
c
t
Reaction conditions: 4-chlorobenzonitrile (1.2 mmol), 4-chlorothiophenol (1 mmol), NaO Bu
o
(
2 equiv.), catalyst (10 mol %) and L-proline (10 mol %) in CH
3
CN for 16 h at 85 C.
d
t
Reaction conditions: 4-bromobenzonitrile (1.2 mmol), 4-chlorothiophenol (1 mmol), NaO Bu
2 equiv.), catalyst (10 mol %) and L-proline (10 mol %) in CH CN for 16 h at 85 C.
3
o
(
4

ACCEPTED MANUSCRIPT
Research Highlights
•
First tetranuclear bismuth anionic salt of semi-super bulky diselenide has been
synthesized and characterized.
•
•
New structural motif for anionic tetranuclear bismuth(III) chloride has been reported.
The catalytic application of tetranuclear bismuth cluster in C-S cross coupling reaction
has been reported.