Investigating intermolecular bonding in diphenylbismuth(III) chalcogenolates: X-ray crystal structures of (Ph2BiSR′) (R′ = Ph; 2,6-Me2C6H3)

Article abstract of DOI:10.1016/j.poly.2011.11.011

The reaction of Ph₂BiCl with (PhS)Li or (2,6-Me ₂C₆H₃S)Li yielded [Ph₂BiSPh] _∞ (7) or Ph₂BiS(2,6-Me₂C ₆H₃)] (8), respectively. Both compounds have been characterized by elemental analysis, melting point, FT-IR, FT-Raman, solution ¹H and ¹³C{¹H} NMR, and X-ray crystallography. The solid-state structure of 7 is polymeric via long intermolecular Bi...S interactions and μ-SPh groups, yielding a distorted ψ-trigonal bipyramidal C₂S₂ bonding environment for bismuth. Increasing steric bulk at the phenyl thiolate ligand in 8 results in the isolation of a monomeric species, which exhibits a distorted ψ-tetrahedral C₂S bonding environment for bismuth. Comparison to previously reported structures of diorganobismuth chalcogenolates shows the effect of altering the chalcogen on intermolecular Bi...E (E = O, S, Se) bond formation. DFT calculations are employed to rationalize the bonding environments at bismuth and the observed polymeric structures. This work represents the first examples of structurally characterized R₂BiSR′ species and advances our understanding of intermolecular bonding in bismuth chalcogenolates.

Full text of DOI:10.1016/j.poly.2011.11.011

Polyhedron 31 (2012) 796–800
Contents lists available at SciVerse ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Investigating intermolecular bonding in diphenylbismuth(III) chalcogenolates:
X-ray crystal structures of (Ph2BiSR0) (R0 = Ph; 2,6-Me2C6H3)
b
a
a
a
Glen G. Briand a, , Andreas Decken , Nicole M. Hunter , Graham M. Lee , Jennifer A. Melanson ,
⇑
Evan M. Owen a
a Department of Chemistry and Biochemistry, Mount Allison University, Sackville, New Brunswick, Canada E4L 1G8
b Department of Chemistry, University of New Brunswick, Fredericton, New Brunswick, Canada E3B 6E2
a r t i c l e i n f o
a b s t r a c t
Article history:
The reaction of Ph2BiCl with (PhS)Li or (2,6-Me2C6H3S)Li yielded [Ph2BiSPh] (7) or Ph2BiS(2,6-Me2C6H3)]
1
Received 16 September 2011
Accepted 14 November 2011
Available online 20 November 2011
(8), respectively. Both compounds have been characterized by elemental analysis, melting point, FT-IR,
FT-Raman, solution 1H and 13C{1H} NMR, and X-ray crystallography. The solid-state structure of 7 is poly-
meric via long intermolecular Biꢀ ꢀ ꢀS interactions and
ramidal C2S2 bonding environment for bismuth. Increasing steric bulk at the phenyl thiolate ligand in 8
results in the isolation of a monomeric species, which exhibits a distorted -tetrahedral C2S bonding
l–SPh groups, yielding a distorted w-trigonal bipy-
Keywords:
Bismuth
S ligands
X-ray diffraction
Density functional calculations
w
environment for bismuth. Comparison to previously reported structures of diorganobismuth chalcogen-
olates shows the effect of altering the chalcogen on intermolecular Biꢀ ꢀ ꢀE (E = O, S, Se) bond formation.
DFT calculations are employed to rationalize the bonding environments at bismuth and the observed
polymeric structures. This work represents the first examples of structurally characterized R2BiSR0 spe-
cies and advances our understanding of intermolecular bonding in bismuth chalcogenolates.
Ó 2011 Elsevier Ltd. All rights reserved.
1. Introduction
Although lower melting points for thiolate versus alkoxide deriva-
tives [11] suggest weak intermolecular bonding interactions in the
There has been increasing interest in heavier main group ele-
ment compounds as synthons for supramolecular systems, due
to their tendency to form strong, reversible and directional sec-
ondary bonding interactions [1]. For example, bismuth chalcogen-
olates [(RE)3Bi]n exhibit extensive intermolecular Biꢀ ꢀ ꢀE bonding
(E = O, S, Se) in the solid-state, which typically results in high coor-
dination numbers for bismuth and complex polymeric structures
[2–5]. Diorganobismuth chalcogenolates ([R2BiER0]n) (E = O, S, Se)
are excellent candidates for investigating Biꢀ ꢀ ꢀE bonding interac-
tions, as they provide individual molecular Bi–E units and limited
intermolecular bonding as compared to tris–chalcogenolate spe-
cies. Structural characterization of diorganobismuth alkoxides
(R2BiOR0) [Et2BiOPh]1 (1), [Et2BiO(C6F5)]1 (2) [6], [Ph2BiOEt]1
solid-state, no simple R2BiSR0 species have been structurally char-
acterized. In this context, we now report the preparation and
structural characterization of [Ph2BiSPh]1 (7) and Ph2BiS(2,6-
Me2C6H3) (8) for comparison of intermolecular Biꢀ ꢀ ꢀE bonding
properties to those of [R2BiER0]n (E = O, Se) species 1–6. Further,
we have performed DFT calculations of Ph2BiEPh (E = O, S, Se)
and Ph2BiS(2,6-Me2C6H3) to investigate intramolecular Bi–E and
intermolecular Biꢀ ꢀ ꢀE bonding in bismuth chalcogenolate
compounds.
(3) [7], [Me2BiOMe] (4) [8] and [(o-tolyl)2BiOMe] (5) [9] has re-
1
1
vealed strong intermolecular Biꢀ ꢀ ꢀO interactions and polymeric
structures. With respect to heavier chalcogen analogs (i.e.
[R2BiER0]n where E = S or Se), the only structurally characterized
example is Ph2BiSePh (6) [10], which is essentially monomeric in
the solid-state and exhibits no Biꢀ ꢀ ꢀSe intermolecular interactions.
⇑
Corresponding author. Tel.: +1 506 364 2346; fax: +1 506 364 2313.
E-mail address: gbriand@mta.ca (G.G. Briand).
0277-5387/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2011.11.011

G.G. Briand et al. / Polyhedron 31 (2012) 796–800
797
axial positions [S1–Bi–S1⁄ = 154.98(4)°], and the two phenyl
carbon atoms [C1–Bi–C7 = 93.99(20)°] and the lone pair in equato-
rial positions. The Bi–C bond distances [Bi–C1 = 2.249(5) Å;
Bi–C7 = 2.248(5) Å] are similar to those in other –BiPh2 compounds
[2.24(5)–2.27 (2) Å] [12]. The Bi–S1 bond distance [2.588(1) Å] is
within the range reported for other bismuth arylthiolates
[2.55(2)–2.634(5)] [13,14], while the Bi–S1⁄ bond distance is sig-
nificantly longer [3.309(1) Å]. The latter is, however, within the
sum of the van der Waals radii of Bi and S (ꢁ3.8 Å) [15], and similar
to intermolecular Biꢀ ꢀ ꢀS contacts found in [(RS)3Bi]n compounds
[3.323(2)–3.583(1) Å] [3,16]. The two phenyl rings on bismuth
are near perpendicular to one another, and are rotated such that
one [C1–C6] is nearly coplanar with the phenyl ring [C13–C18] of
the more closely bonded thiolate group.
Unlike 7, the structure of Ph2BiS(2,6-Me2C6H3) (8) (Fig. 2) shows
the compound to be monomeric in the solid-state. The nearest
Biꢀ ꢀ ꢀS1⁄ intermolecular contact in 8 is 3.940(2) Å, which is outside
of the sum of the van der Waals radii of Bi and S, and there is a dif-
ferent packing arrangement of the molecules as compared to 7.
This results in a three-coordinate C2S bonding environment and a
2. Results and discussion
2.1. Syntheses
The reaction of Ph2BiCl with (PhS)Li or (2,6-Me2C6H3S)Li re-
sulted in an immediate yellow colored reaction mixture, indicative
of the formation of a bismuth thiolate. Both reactions were com-
plete within three hours as determined via 1H NMR spectra of reac-
tion mixtures. Crystalline products were isolated from reaction
mixture (8) or after removal of the reaction solvent and extraction
into methanol (7). Reported yields are for isolated crystalline mate-
rials. Attempts to prepare Ph2BiTePh via the reaction of Ph2BiCl and
PhTeLi at low temperature resulted in the precipitation of elemen-
tal tellurium upon warming of the reaction mixture to room tem-
perature [5].
2.2. X-ray crystal structures
Crystals suitable for X-ray crystallography were isolated from
methanol at 4 °C (7), or by the slow evaporation of the thf reaction
mixture at 23 °C (8). Selected bond distances and angles are given
in Table 1.
The crystal structure of [Ph2BiSPh] (7) (Fig. 1) shows the com-
pound to be a zig–zag polymer in the solid-state via bridging l-SPh
groups, giving a four coordinate C2S2 bonding environment and a
distorted disphenoidal geometry at bismuth. If the stereochemi-
cally active lone pair is considered, the metal bonding environment
distorted
w-tetrahedral geometry at bismuth [sum of angles
ꢁ281°]. The Bi–C bond distances [Bi–C1 = 2.262(4) Å; Bi–C7 =
2.245(5) Å] are similar to those in 7. The Bi–S1 distance
[2.544(2) Å] is significantly shorter, and at the low. This is presum-
ably due to the lower coordination number of bismuth and the
absence of the trans influence of S1⁄, as observed in 7 (vide infra).
Comparison of the Bi-S-C bond angles in 7 and 8 shows the former
to be much larger [7: Bi1–S1–C13 = 107.8(2)°; 8: Bi1–S1–C13 =
98.3(1)°].
1
is
w-trigonal bipyramidal, with the two thiolate sulfur atoms in
2.3. Comparison to previously reported [R2BiER0]n (E = O, Se) structures
Table 1
Selected bond distances (Å) and angles (deg) for 6–7.
The R2BiOR0 compounds 1–4 all show polymeric structures via
6
7
intermolecular Biꢀ ꢀ ꢀO interactions, with distorted
w-trigonal bipy-
Bi1–C1
Bi1–C7
2.248(5)
2.248(5)
2.588(1)
3.309(1)
94.0(2)
2.262(4)
2.245(4)
2.545(1)
ramidal C2E2 bonding environments at bismuth, and oxygen atoms
in axial positions (Table 2) [6–8]. The Bi–O bonds are equal within
esd values in 1, 2 and 4, and differ by only ꢁ0.02 Å (ꢁ1%) in 3. Com-
pound 5 features a relatively acute O–Bi–O⁄ bond angle [123.7(3)°],
and a ꢁ0.1 Å (ꢁ4%) difference in Bi–O bond distances [9]. In all
cases, Bi–O bond distances are short and intermolecular contacts
may be considered strong [17,18]. The Bi–S bond distances in 7 dif-
fer by ꢁ0.75 Å (ꢁ28%), and the polymeric structure may be consid-
ered weakly associated. Interestingly, the selenolate analog 6
crystallizes in the same space group as 7 [P2(1)2(1)2(1)], and the
molecules are packed in a similar (polymeric) arrangement [10].
However, the Bi–Se and Biꢀ ꢀ ꢀSe⁄ distances in 6 differ by ꢁ1.19 Å
(ꢁ44%). Further, the intermolecular Biꢀ ꢀ ꢀSe⁄ distance [3.897(3) Å;
sum of van der Waals radii of ꢁ3.9 Å)] [16] is greater than those
Bi1–S1
Bi1–S1⁄
C1–Bi1–C7
C1–Bi1–S1
C7–Bi1–S1
C13–S1–Bi1
S1–Bi1–S1⁄
Bi1–S1–Bi1⁄
C1–Bi–S–C13
C7–Bi–S–C13
92.6(2)
92.2(1)
96.1(1)
98.3(1)
82.8(1)
95.4(2)
107.8(2)
154.98(4)
116.42(5)
170.1(2)
ꢂ96.5(2)
ꢂ142.9(2)
124.3(2)
observed in polymeric [(RSe)3Bi] species [3.466(1)–3.572(2) Å]
1
[16]. This suggests there are no intermolecular Biꢀ ꢀ ꢀSe contacts
and that 6 is monomeric in the solid-state.
Fig. 1. X-ray structure of 7 (30% probability ellipsoids). Hydrogen atoms are not
shown for clarity. Symmetry transformations used to generate equivalent atoms:
(ꢃ) x ꢂ 0.5, ꢂy + 1.5, ꢂz; (ꢃꢃ) x + 0.5, ꢂy + 1.5, ꢂz.
Fig. 2. X-ray structure of 8 (30% probability ellipsoids). Hydrogen atoms are not
shown for clarity.

798
G.G. Briand et al. / Polyhedron 31 (2012) 796–800
Table 2
Selected bond distances (Å) and angles (deg) for polymeric structures 1–7.
1
2
3
4
5
6
7
Bi–E
2.382(7)
2.382(7)
81.2(9)
179.0(3)
115.38(3)
2.4105(7)
2.4105(7)
80.0(2)
179.54(4)
113.57(2)
2.327(2)
2.400(2)
94.6(1)
176.27(3)
125.04(9)
2.344(6)
2.359(6)
96.3(4)
170.2(1)
123.4(3)
2.295(5)
2.399(5)
96.2(2)
123.7(3)
123.7(3)
2.704(3)
3.897(3)
90.8(4)
176.75(7)
84.76(7)
2.588(1)
3.309(1)
94.00(2)
154.98(4)
116.42(5)
Biꢀ ꢀ ꢀE⁄
C–Bi–C
E–Bi–E⁄
Bi–E–Bi⁄
1–5: E = O; Refs [6–9].
6: E = Se; Ref [10].
7: E = S; this work.
2.4. DFT studies
Table 3
DFT calculated orbital energies (eV) and Mulliken atomic charges (eꢂ).
To probe bonding at bismuth and further examine intermolecu-
lar Biꢀ ꢀ ꢀE bonding interactions, we have performed DFT calcula-
tions of the monomeric structures Ph2BiEPh [E = O, S, Se] and
Ph2BiS(2,6-Me2C6H3). Representations of the geometry-optimized
structures and selected molecular orbitals of Ph2BiSPh and
Ph2BiS(2,6-Me2C6H3) are shown in Fig. 3 (others are found in the
Supplementary data). Calculated energies of the frontier molecular
orbitals (eV) and Mulliken atomic charges (eꢂ) of Bi and E for all
compounds are given in Table 3. A comparison of bond distances
and angles show that the geometry optimized structures resemble
those of corresponding compounds in the solid-state (see Supple-
mentary data). Important structural differences are highlighted in
the discussion below.
Ph2BiOPh
Ph2BiSPh
Ph2BiS(2,6-Me2C6H3)
Ph2BiSePh
LUMO
HOMO
HOMOꢂ1
q(Bi)
ꢂ1.35
ꢂ5.53
ꢂ6.67
0.90
ꢂ1.42
ꢂ5.90
ꢂ6.48
0.63
ꢂ1.42
ꢂ6.03
ꢂ6.06
0.63
ꢂ1.39
ꢂ5.76
ꢂ6.35
0.66
q(E)
ꢂ0.72
ꢂ0.20
ꢂ0.20
ꢂ0.31
The calculated Bi–S bond distance (2.58 Å) in Ph2BiSPh is very
similar to the solid-state structure of 7 [2.588(1) Å], which is unex-
pected given the absence of a trans influence of a Biꢀ ꢀ ꢀS intermolec-
ular contact in the geometry optimized monomer (vide infra). A
similar Bi–S bond distance is calculated for Ph2BiS(2,6-Me2C6H3)
[2.58 Å], though the value in the solid-state structure is slightly
smaller [8: 2.545(1) Å]. The most significant difference in the poly-
meric solid-state and monomeric calculated structures of Ph2BiSPh
is the Bi-S-C bond angle [7: Bi1–S1–C13 = 107.8(2)°; calcu-
late = 100.5°]. Again, a similar value (101.1°) is calculated for
Ph2BiS(2,6-Me2C6H3), which is much closer to the experimental va-
lue for 8 [Bi1–S1–C13 = 98.3(1)°].
Analysis of the frontier molecular orbitals and MO coefficients
of Ph2BiSPh shows that the LUMO is a Bi(6p)–S(3p)
r-antibonding
orbital, the HOMO is Bi(6p)–S(3p) -bonding orbital, the
a
r
HOMOꢂ1 represents a S(3p) lone pair, and the HOMOꢂ2 repre-
sents the Bi lone pair (Fig. 3). It is clear from the orientation of
the LUMO and HOMOꢂ1 that these are the electron acceptor and
donor orbitals, respectively, that are involved in intermolecular
Biꢀ ꢀ ꢀS bonding observed in the solid-state structure of 7 (Figs. 1
and 4). Analysis of the frontier molecular orbitals of Ph2BiS(2,6-
Me2C6H3) shows similar LUMO, HOMO and HOMOꢂ1 orbitals to
Ph2BiSPh, with the HOMOꢂ3 representing the Bi lone pair. The
S(3p) lone pair (HOMOꢂ1) is coplanar with the benzenethiolate
ring and is oriented toward the 2,6-methyl groups. This suggests
that the nominal sterics provided by the benzenethiolate methyl
groups preclude intermolecular Biꢀ ꢀ ꢀS bonding in 8.
Geometry optimized structures of Ph2BiOPh and Ph2BiSePh
show similar structural arrangements and frontier molecular orbi-
tals to that of Ph2BiSPh. In the case of Ph2BiOPh, however, the
O(2p) lone pair is the HOMO versus the HOMOꢂ1. In the absence
of a trans intermolecular Biꢀ ꢀ ꢀO contact, the calculated Bi–O bond
Fig. 3. DFT geometry-optimized structures and selected molecular orbitals of
Ph2BiSPh and Ph2BiS(2,6-Me2C6H3).
Fig. 4. Schematic representation of orbital overlap responsible for intermolecular
Biꢀ ꢀ ꢀE bonding in R2BiER0 yielding a zig–zag polymeric arrangement.

G.G. Briand et al. / Polyhedron 31 (2012) 796–800
799
distance in Ph2BiOPh of 2.14 Å is significantly shorter that that ob-
served in structures 1–5 [2.295(5)–2.4105(7) Å; Table 2] [6–9].
and 50.3 MHz, respectively), and chemical shifts are calibrated to
the residual solvent signal. FT-IR spectra were recorded as Nujol
mulls with NaCl plates on a Mattson Genesis II FT-IR spectrometer
in the range of 4000–400 cmꢂ1. FT-Raman spectra were recorded
on a Thermo Nicolet NXR 9600 Series FT-Raman spectrometer in
the range 3900–70 cmꢂ1. Melting points were recorded on an Elec-
trothermal MEL-TEMP melting point apparatus and are uncor-
rected. Elemental analyses were performed by Chemisar
Laboratories Inc., Guelph, Ontario.
This supports the identification of the LUMO Bi(6p)–E(np)
r-anti-
bonding orbital as the electron acceptor in Ph2BiEPh intermolecu-
lar Biꢀ ꢀ ꢀE interactions. The Bi-Se bond distance in Ph2BiSePh is
similar in the calculated and solid-state (6) structures [2.69 Å
and 2.704(3), respectively], while the calculated Bi–Se–C bond an-
gle (97.5°) is only slightly more acute than in the solid-state struc-
ture [100.0(4)°]. The lack of an increase in Bi–Se bond distance and
Bi–Se–C angle in the solid-state structure of 6 versus the calculated
structures further suggests the absence of significant intermolecu-
lar Biꢀ ꢀ ꢀSe contacts.
4.2. Preparation of Ph2BiSPh (6)
Although the LUMO energy of Ph2BiOPh is similar to Ph2BiSPh,
the energy of the O(2p) lone pair (HOMO) is significantly higher
than that of the S(3p) lone pair (HOMOꢂ1) (Table 3). Further, the
difference in the Mulliken atomic charges of Bi and E is much larger
for Ph2BiOPh (1.62 eꢂ) as compared to Ph2BiSPh (0.82 eꢂ) or Ph2Bi-
SePh (0.96 eꢂ). This suggests that strong intermolecular Biꢀ ꢀ ꢀO
bonding observed in [R2BiOR0]n (1–5) is influenced by more effec-
tive orbital overlap and larger electrostatic interactions. Given
the relative similarity of LUMO/HOMOꢂ1 frontier orbital energies
and Bi/S and Bi/Se Mulliken atoms charges in Ph2BiEPh (E = S,
Se), the absence of intermolecular interactions in Ph2BiSePh is pre-
sumably due to poor Bi(6p)–Se(4p) orbital overlap.
LiSC6H5 (0.100 g, 0.530 mmol) was added to a suspension of
Ph2BiCl (0.211 g, 0.530 mmol) in tetrahydrofuran (10 mL). The
reaction mixture turned from cloudy white to cloudy yellow with-
in seconds. The reaction was allowed to stir for 3 h, after which the
solvent was removed in vacuo and the remaining solid extracted
with methanol (5 mL). The mixture was then filtered and allowed
to sit at 4 °C for 1 d, after which yellow crystals of 6 were collected
by filtration (0.034 g, 0.072 mmol, 14%). M.p. 102 °C. Anal. Calc. for
C
18H15BiS: C, 45.77; H, 3.20; N, 0.00. Found: C, 46.44; H, 3.28; N,
0.00%. FT-Raman (cmꢂ1): 114 m, 168 vs, 194 w, 212 w, 244 s,
339 vs, 419 m, 480 vw, 615 vw, 645 m, 696 w, 998 vs, 1017 w,
1081 m, 1117 w, 1155 w, 1187 w, 1264 vw, 1328 vw, 1433 vw,
1473 w, 1572 m, 3042 s, 3135 w. FT-IR (cmꢂ1): 688 m, 721 m,
735 m, 955 w, 1020 w, 1055 w, 1078 w, 1119 vw, 1157 w, 1263
vw, 1296 w, 1431 m, 1568 m, 1622 w, 1651 w, 1718 w. NMR data
(thf-d8): 1H NMR, d = 7.00 (m, 1H, Ph2BiSPh), 7.09 (m, 2H,
3. Conclusions
The formation of a polymeric structure for 7 and a monomeric
structure for 8 in the solid-state demonstrates that a modest
amount of steric bulk at sulfur is sufficient to preclude intermolec-
ular Biꢀ ꢀ ꢀS bonding in bismuth-thiolate species. DFT studies of
3
Ph2BiSPh), 7.27–7.32 (m, 4H, Ph2BiSPh), 7.49 (t, JH–H = 5.7 Hz, 4H,
Ph2BiSPh), 8.15 (d, JH–H = 5.3 Hz, 4H, Ph2BiSPh). 13C {1H} NMR,
3
d = 125.4 (s, Ph2BiSPh), 127.7 (s, Ph2BiSPh), 128.1 (s, Ph2BiSPh),
130.9 (s, Ph2BiSPh), 134.4 (s, Ph2BiSPh), 137.3 (s, Ph2BiSPh).
Ph2BiEPh (E = O, S, Se) rationalize the observed
w-trigonal bipyra-
midal metal bonding environments and zig–zag arrangement of
solid-state polymeric structures, as well as the observed Eꢀ ꢀ ꢀBi–E
trans influence. Analysis of atomic charges shows the significance
of electrostatic interactions in forming strong intermolecular Biꢀ ꢀ ꢀE
4.3. Preparation of Ph2BiS(2,6-Me2C6H3) (7)
LiS(2,6-Me2C6H3) (0.090 g, 0.627 mmol) was added to a suspen-
sion of Ph2BiCl (0.250 g, 0.627 mmol) in methanol (10 mL) to give a
clear yellow solution. The reaction mixture was allowed to stir for
3 h, filtered, and the filtrate was allowed to sit at 23 °C. After 1 d yel-
low crystals of 7 were collected by filtration (0.030 g, 0.060 mmol,
10%). M.p. 104 °C. Anal. Calc. for C20H19BiS: C, 48.00; H, 3.83; N,
0.00. Found: C, 48.61; H, 3.93; N, 0.00%. FT-IR (cmꢂ1): 692 w, 723
m, 766 vw, 800 vw, 845 w, 997 vw, 1016 vw, 1049 vw, 1109 vw,
1155 vw, 1589 w. FT-Raman (cmꢂ1): 110 vs, 140 m, 155 m, 188 s,
209 s, 223 m, 244 s, 331 s, 418 m, 534 w, 589 m, 615 w, 645 s,
726 vw, 766 m, 853 vw, 910 w, 997 vs, 1016 m, 1051 m, 1156 w,
1171 w, 1186 w, 1250 m, 1327 vw, 1375 vw, 1427 w, 1455 vw,
1474 w, 1568 m, 1583 m, 2908 m, 2941 w, 2975 w, 3035 s, 3133
w. NMR data (thf-d8): 1H NMR, d = 2.37 (s, 6H, Ph2BiS-2,6-Me2C6H3),
bonds in [R2BiOR0] species, as compared to thiolate and selenolate
1
analogs. Computational studies of Ph2BiS(2,6-Me2C6H3) confirm
that the absence of intermolecular bonding in 8 is a result of the
orientation of the HOMOꢂ1 lone pair of the thiolate sulfur atom to-
ward the 2,6-dimethyl substituents. This work represents the first
examples of structurally characterized R2BiSR0 species, and ad-
vances our understanding of covalent and intermolecular Bi–E
(E = O, S, Se) bonding in bismuth chalcogenolates.
4. Experimental
4.1. General considerations
6.86 (m, 1H, Ph2BiS-2,6-Me2C6H3), 7.00 (m, 2H, Ph2BiS-2,6-
3
Bismuth(III) chloride (99.999%), benzenethiol (P98%), 2,6-dim-
ethylbenzenthiol (95%), and n-butyllithium (1.6 M in hexanes)
were used as received from Aldrich. Triphenylbismuth (99.999%)
was used as received from Strem. Methanol, tetrahydrofuran and
diethyl ether were dried using an MBraun SPS column solvent puri-
fication system. Ph2BiCl was prepared by literature procedures
from the 2:1 reaction of Ph3Bi and BiCl3 in thf [19]. Lithium ben-
zenethiolates were prepared via the reaction of the appropriate
benzenethiol with a stoichiometric amount of n-BuLi (1.6 M in
hexanes) in diethyl ether at 23 °C, followed by solvent removal in
vacuo. Products were used without further purification. All reac-
tions were carried out under dinitrogen atmosphere using stan-
dard Schlenk techniques.
Me2C6H3), 7.28 (m, 2H, Ph2BiS-2,6-Me2C6H3), 7.48 (t, JH–H
=
5.3 Hz, 4H, Ph2BiS-2,6-Me2C6H3), 8.12 (m, 4H, Ph2BiS-2,6-Me2C6H3).
13C{1H} NMR, d = 23.0 (s, Ph2BiS-2,6-Me2C6H3), 125.9 (s, Ph2BiS-2,
6-Me2C6H3), 128.0 (s, Ph2BiS-2,6-Me2C6H3), 130.2 (s, Ph2BiS-2,
6-Me2C6H3), 130.7 (s, Ph2BiS-2,6-Me2C6H3), 137.4 (s, Ph2BiS-2,6-
Me2C6H3), 143.1 (s, Ph2BiS-2,6-Me2C6H3).
4.4. X-ray crystallography
Crystals of 7 and 8 suitable for X-ray crystallography were pre-
pared as indicated above. Single crystals were coated with Par-
atone-N oil, mounted using a polyimide MicroMount and frozen
in the cold nitrogen stream of the goniometer. A hemisphere of
data was collected on a Bruker AXS P4/SMART 1000 diffractometer
Solution 1H and 13C{1H} NMR spectra were recorded at 23 °C on
a JEOL GMX 270 MHz spectrometer (270.2 and 67.9 MHz, respec-
tively) or a Varian MERCURYplus 200 MHz spectrometer (200.0
using
x and h scans with a scan width of 0.3° and 10 s exposure
times. The detector distance was 5 cm. The data were reduced

800
G.G. Briand et al. / Polyhedron 31 (2012) 796–800
Table 4
Appendix A. Supplementary data
Crystallographic data for 7 and 8.
7
8
CCDC 836302 and 836303, contains the supplementary crystal-
lographic data for 7 and 8. These data can be obtained free of
charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or
from the Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336 033; or e-mail: depos-
it@ccdc.cam.ac.uk. Supplementary data associated with this article
can be found, in the online version, at doi:10.1016/j.poly.
2011.11.011.
Formula
C
18H15BiS
C20H19BiS
500.39
triclinic
Formula weight
Crystal system
Space group
a (Å)
b (Å)
c (Å)
472.34
orthorhombic
P2(1)2(1)2(1)
9.6228(16)
9.9948(17)
16.399(3)
90
90
90
1577.3(5)
4
888
ꢀ
P1
5.4890(6)
12.129(1)
14.050(2)
70.754(1)
86.530(1)
88.857(1)
881.5(2)
2
476
1.885
10.113
198(1)
0.71073
0.0270
a
(deg)
b (deg)
c
(deg)
References
V (Å3)
Z
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F(000)
qcalc. (g cmꢂ3
)
1.989
l
(mmꢂ1
)
11.298
198(1)
0.71073
0.0246
0.0613
T (K)
k (Å)
a
R1
b
wR2
0.0705
a
R1 = [
R
||Fo| ꢂ |Fc||]/[
R
|Fo|] for [Fo2 > 2
r
(Fo2)].
b
2
½
wR2 = {[
R
w(Fo ꢂ Fc2)2]/[
R
w(Fo4)]}
.
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(
SAINT) [20] and corrected for absorption (SADABS) [21]. The struc-
tures were solved by direct methods and refined by full-matrix
least squares on F2
SHELXTL) [22] on all data. All non-hydrogen
(
atoms were refined using anisotropic displacement parameters.
Hydrogen atoms were included in calculated positions and refined
using a riding model. Crystallographic data are given in Table 4.
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689 (2004) 3012.
4.5. Computational methods
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451.
DFT calculations were performed using GAUSSIAN 09 at the B3LYP
6-31G⁄ level of theory for all atoms except Bi, for which Stuttgart
electron core pseudo-potentials (sdd) were employed [23]. All
structures were geometry optimized and structural parameters
for input files were derived from crystal structure data where pos-
sible. Structural parameters for proposed monomeric structures
were derived from the crystal structure data of 6. Frequency calcu-
lations were performed on all structures and gave no imaginary
frequencies. Molecular orbital representations and structural
parameters are given in the Supplementary data.
[19] D.H.R. Barton, N.Y. Bhatnagar, J.-P. Finet, W.B. Motherwell, Tetrahedron 42
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[20] SAINT 7.23A, Bruker AXS, Inc., Madison, Wisconsin, USA, 2006.
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G. Scalmani, V. Barone, B. Mennucci, G.A. Petersson, H. Nakatsuji, M. Caricato,
X. Li, H.P. Hratchian, A.F. Izmaylov, J. Bloino, G. Zheng, J.L. Sonnenberg, M.
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C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R.
Cammi, C. Pomelli, J.W. Ochterski, R.L. Martin, K. Morokuma, V.G. Zakrzewski,
G.A. Voth, P. Salvador, J.J. Dannenberg, S. Dapprich, A.D. Daniels, O. Farkas, J.B.
Acknowledgements
We thank the following: Dan Durant for assistance in collecting
solution NMR data; and the Natural Sciences and Engineering Re-
search Council of Canada, the New Brunswick Innovation Founda-
tion, the Canadian Foundation for Innovation and Mount Allison
University for financial support.
Foresman, J.V. Ortiz, J. Cioslowski, D.J. Fox, GAUSSIAN 09, Revision B.01, GAUSSIAN
Inc., Wallingford CT, 2010.
,