A structural investigation of dimethylthallium(III) thiolate and selenolate rings and polymers

Article abstract of DOI:10.1002/ejic.201100773

The effects of increased steric bulk in dimethylthallium(III) chalcogenolates on oligomerization was examined. The facile reaction of Me ₃Tl with a series of benzenethiols and-selenols in toluene or thf resulted in the formation of [Me₂

Full text of DOI:10.1002/ejic.201100773

FULL PAPER
DOI: 10.1002/ejic.201100773
A Structural Investigation of Dimethylthallium(III) Thiolate and Selenolate
Rings and Polymers
Glen G. Briand,*[a] Andreas Decken,[b] Nicole M. Hunter,[a] John A. Wright,[a] and
Y. Zhou[a]
Keywords: Thallium / Selenium / S ligands / Se ligands / Structure elucidation / Chalcogens
The effects of increased steric bulk in dimethylthallium(III)
chalcogenolates on oligomerization was examined. The fac-
ile reaction of Me3Tl with a series of benzenethiols and -sele-
nols in toluene or thf resulted in the formation of
[Me2TlS(2,6-Me2C6H3)]ϱ (2), [Me2TlS(2,4,6-tBu3C6H2)]ϱ (3),
[Me2TlSe(C6H5)]2 (4), [Me2TlSe(2,4,6-Me3C6H2)]ϱ (5), and
[Me2TlSe(2,4,6-tBu3C6H2)]ϱ (6). The solid-state structure of 4
is dimeric with short intermolecular Tl···Se interactions,
which yields an asymmetric Tl2Se2 core and a distorted tetra-
hedral C2Se2 bonding environment for the thallium. The in-
crease in the steric bulk of the chalcogenolate ligand in com-
pounds 2 and 5 results in the formation of polymeric struc-
tures with μ-E[2,(4),6-Me3C6H2] (E = S, Se) groups and dis-
torted tetrahedral C2E2 bonding environments for the thal-
lium. A further increase in the steric bulk of the phenylchal-
cogenolate resulted in the formation of chains of weakly co-
ordinated monomers by means of the intermolecular Tl···E
interactions in 3 (E = S) and 6 (E = Se). This work represents
the first systematic study of diorganothallium thiolates and
selenolates and compounds 4–6 represent the first structur-
ally characterized examples of R2TlSeRЈ species. A compari-
son of the structures of [Me2TlS(C6H5)]2 (1) and 2–6 with
other group 13 analogue structures suggests that the degree
of oligomerization differs for [Me2MSRЈ]n (M = Tl) versus the
analogous (M = Al, Ga, and In) species. These findings are
important in understanding the factors that govern oligomeri-
zation (i.e. ring size) and polymerization of diorganotriel
chalcogenolates.
Me3C6H2, 2,4,6-tBu3C6H2] expanded this series to include
monomeric (n = 1) and weakly associated polymeric (n =
1, ϱ) structures.[11,12]
Introduction
Inorganic rings and polymers of the p-block elements
continue to be extensively studied due to their interesting
structural and bonding properties, as well as their applica-
tions as precursors for useful materials.[1,2] In particular, the
diorganochalcogenolate compounds of the group 13 ele-
ments [R2MERЈ]n (where M = Al, Ga, In and E = S, Se,
Te; M = Tl and E = O) have been studied for a number of
years as potential precursors for the fabrication of group 13
to 16 semiconducting thin films by means of various chemi-
cal vapor deposition techniques.[3–6] Structural studies have
shown that the vast majority of these compounds are di-
meric in the solid-state (Figure 1, n = 2).[7] However, exam-
ples of oligomeric (n = 3, 4) and polymeric (n = ϱ) struc-
tures have been observed for the dimethyltriel thiolate
[Me2MSRЈ]n compounds, such as [Me2InStBu]3,
[Me2MS(2,6-Me2C6H3)]4 (M = Al, Ga, In), and [Me2-
AlSPh]ϱ.[8–10] Our studies of [Me2InERЈ]n (E = O, S, Se)
and [Me2TlORЈ]n species that incorporated chalcogenolate
ligands with varying steric bulk [RЈ = C6H5, 2,(4),6-
Figure 1. The schematic drawings of the possible oligomers of
[R2MERЈ]n.
[a] Department of Chemistry and Biochemistry, Mount Allison
University,
Despite the extensive number of studies that have been
devoted to this class of compounds, the diorganothallium
selenolate analogues [R2TlSeRЈ]n are virtually unknown.
Furthermore, structural studies of the simple diorganothal-
lium thiolate analogues [R2TlSRЈ]n (i.e. where RЈ does not
Sackville, New Brunswick, E4L 1G8, Canada
Fax: +1-506-364-2313
E-mail: gbriand@mta.ca
[b] Department of Chemistry, University of New Brunswick,
Fredericton, New Brunswick, E3B 6E2, Canada
5430
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Dimethylthallium(III) S and Se Rings and Polymers
possess donor atoms) are limited to [Me2TlSPh]2 (1), which 40.6 ppm), and the coupling constants (2JH,Tl = 346–
1
exhibits a dimeric (n = 2) structure in the solid-state and 372 Hz; JC,Tl = 2225–3434 Hz) do not correspond to the
an asymmetric Tl2S2 core.[13] The Me2TlEMe (E = S, Se) changes in the CMe–Tl–CMe bond angle or the Tl–E bond
compounds were also reported some time ago but were lengths observed in the solid-state structures (vide infra).
characterized by elemental analysis and molecular weight
determination only, the latter of which suggested that they
X-ray Crystal Structures
are both dimeric in the solid-state.[14,15] To further expand
Crystals that were suitable for X-ray crystallographic
analysis were isolated for compounds 2–6 by the slow evap-
oration of the reaction mixtures at 23 °C. The selected bond
lengths and angles for 1 and 3 to 6 are given in Table 1.
our previous studies of the [Me2TlORЈ]n species, and in or-
der to compare their structures with those of the Al, Ga,
and In analogous, we have synthesized and structurally
characterized [Me2TlS(2,6-Me2C6H3)]ϱ (2), [Me2TlS(2,4,6-
tBu3C6H2)]ϱ (3), [Me2TlSe(C6H5)]2 (4), [Me2TlSe(2,4,6-
Me3C6H2)]ϱ (5), and [Me2TlSe(2,4,6-tBu3C6H2)]ϱ (6).
Table 1. The selected bond lengths [Å] and angles [°] for 1 and 3–
6.[a]
1[13]
3
4
5
6
Tl1–C1
Tl1–C2
Tl1–E1
Tl1–E1*
2.10(3)
2.11(3)
2.748(8)
2.991(8)
2.158(4) 2.156(9) 2.173(8)
2.163(5) 2.146(10) 2.167(7)
2.7185(9) 3.1741(9) 2.859(1)
2.156(5)
2.156(5)
2.8057(5)
2.9969(9) 2.848(1) 2.8865(9) 3.0149(5)
C1–Tl1–C2 163.5(9)
E1–Tl1–E1*
Tl1–E1–Tl1*
158.4(2) 164.3(3) 154.9(4) 158.0(2)
120.13(1) 92.64(2) 107.16(2) 115.19(1)
140.64(4) 87.36(2) 119.66(3) 145.16(2)
[a] E = S (1, 3), Se (4–6).
Results and Discussion
Despite several attempts in various solvents, crystals of
[Me2TlS(2,6-Me2C6H3)]ϱ (2) that were of sufficient quality
for the adequate refinement of the X-ray crystallographic
data could not be obtained.[18] However, the preliminary
data was sufficient in order to confirm that the compound
exists as a polymer in the solid-state with bridging μ-S(2,6-
Me2C6H3) groups, which give a four-coordinate C2S2 bond-
ing environment and a distorted tetrahedral geometry at the
thallium.
Syntheses and Spectroscopic Characterization
Compounds 1–6 were prepared by means of a hydro-
carbon elimination reaction between trimethylthallium and
the corresponding thiol or selenol compound. All of the
reactions occurred rapidly at room temperature with the
evolution of methane gas. The reaction mixtures were
stirred for one hour and then filtered in order to remove
any of the precipitated product. The crystalline materials
were isolated by means of slow evaporation of the reaction
mixtures or by means of solvent layering. Although all of
The structure of [Me2TlS(2,4,6-tBu3C6H2)]ϱ (3) (Fig-
ure 2) shows a polymer with μ-S(2,4,6-tBu3C6H2) bridging
1
the reactions were quantitative, as determined by the H
NMR spectra of the reaction mixtures, the reported yields
(28–80%) are for the crystalline material that was obtained
from the reaction filtrate. [Me2TlSPh]2 (1) has been pre-
viously synthesized by the stoichiometric reaction of
(Me2Tl)(CO3) or Me2TlOH with PhSH.[16,17] However,
these syntheses require the preparation of the hydroxide or
carbonate from Me3Tl and are therefore less direct routes
to 1. The attempts to prepare [Me2TlTePh]n by means of
the reaction of Me3Tl and C6H5TeH or Me2TlBr and
C6H5TeLi in thf at –90 °C resulted in the precipitation of
elemental tellurium when the reaction mixtures were
warmed to room temperature.
The FT-Raman spectra of compounds 1–6 show a strong
resonance in the 457 to 474 cm–1 region. This corresponds
to the νsym(Me–Tl–Me) stretching mode and is a character-
istic feature in the spectra of the Me2TlX compounds.[15–17]
Furthermore, the 1H and 13C{1H} NMR spectra show
readily discernible doublet patterns for the Me2TlERЈ reso-
nances as a result of the 2J(1H,203/205Tl) and 1J(13C,203/
205Tl) couplings, respectively. The observed νasym(Me–Tl–
Me) vibrational frequencies, the chemical shift values (1H
Figure 2. The X-ray crystal structure of 3 (30% probability ellip-
soids). The hydrogen atoms are not shown for the sake of clarity.
The symmetry transformations that were used to generate the
equivalent atoms are (*) –x, –0.5 + y, 0.5 – z and (**) –x, 0.5 + y,
NMR, δ = 0.39–1.13 ppm; 13C{1H} NMR δ = 18.0– 0.5 – z.
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G. G. Briand et al.
FULL PAPER
groups. The Tl–S bond lengths are significantly different
[Tl1–S1 2.7185(9) Å, Tl1–S1* 2.9969(9) Å] with the Tl1–
S1* bond approximately 0.18 Å longer than the Tl1–S1
bond. Furthermore, the sum of the C1–Tl1–C2 [158.4(2)°],
C1–Tl1–S1 [97.6(1)°], and C2–Tl1–S1 [100.9(1)°] bond
angles is approximately 357°. This suggests that a distorted
T-shaped C2S bonding environment exists at Tl with a weak
intermolecular Tl···S interaction. The polymeric structure
may therefore be viewed as being composed of weakly asso-
ciated monomers.
The structure of [Me2TlSe(C6H5)]2 (4) (Figure 3) is sim-
ilar to that of 1 and shows that the compound is a dimer
in the solid-state and is linked by means of intermolecular
Tl···Se interactions. It exhibits a four-membered [–Tl–Se–
Tl–Se–] ring core and a distorted tetrahedral C2Se2 bonding
environment for the thallium. Like 1, and unlike the phe-
nolate analogue [Me2TlOPh]2,[12] the Tl–E bond lengths
[Tl1–Se1 3.1741(9) Å, Tl1–Se2 2.848(1) Å] are significantly
different and the structure may be considered a weakly as-
sociated dimer. The sum of the bond angles at Se in 4 is
approximately 297° and the phenyl groups are in a trans
orientation.
Figure 4. The X-ray crystal structure of 5 (30% probability ellip-
soids). The hydrogen atoms are not shown for the sake of clarity.
The symmetry transformations that were used to generate the
equivalent atoms are (*) 1 – x, –y, –0.5 + z and (**) 1 – x, –y, 0.5
+ z.
Figure 3. The X-ray crystal structure of 4 (30% probability ellip-
soids). The hydrogen atoms are not shown for the sake of clarity.
The symmetry transformations that were used to generate the
equivalent atoms are (*) 1 – x, –y, 1 – z.
The X-ray crystal structure of [Me2TlSe(2,4,6-Me3-
C6H2)]ϱ (5) (Figure 4) shows that the compound is a poly-
mer in the solid-state and is linked by means of bridging
μ-Se(2,4,6-Me3C6H2) groups, which gives a four-coordinate
C2Se2 bonding environment and a distorted tetrahedral ge-
ometry at the thallium. The Tl–C [Tl1–C1 2.173(8) Å, Tl1–
C2 2.167(7) Å] and Tl–Se [Tl1–Se1 2.859(1) Å, Tl1–Se1*
2.8865(9) Å] bond lengths are similar to those obtained for
4. However, both the Se1–Tl1–Se1* [107.16(2)°] and Tl1–
Se1–Tl1* [119.66(3)°] bond angles of 5 are significantly
larger than those observed in 4, which is a result of the
polymeric structure of 5 versus the dimeric structure of 4.
The Tl1–E1 and Tl1–E1* bond lengths in 5 [Tl1–Se1
2.859(1) Å, Tl1–Se1* 2.8865(9) Å] are similar and each of
the selenolate groups is equally associated with the two
Figure 5. The X-ray crystal structure of 6 (30% probability ellip-
soids). The hydrogen atoms are not shown for the sake of clarity.
The symmetry transformations that were used to generate the
equivalent atoms are (*) –x, –0.5 + y, 0.5 – z and (**) –x, 0.5 + y,
0.5 – z.
[Me2TlSe(2,4,6-tBu3C6H2)]ϱ (6) (Figure 5) is iso-
neighbouring Tl atoms. The (2,4,6-Me3C6H2) groups alter- structural with 3 and shows a weakly associated polymeric
nate along the [–Tl–Se–]ϱ chain in a syndiotactic-type of structure that is linked by means of the μ-Se(2,4,6-
arrangement.
tBu2C6H3) bridging groups. As in 3, the Tl–E bond lengths
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© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2011, 5430–5436

Dimethylthallium(III) S and Se Rings and Polymers
are significantly different [Tl1–Se1 2.8057(5) Å, Tl1–Se1* structures, while M = Tl has a dimeric structure. In ad-
3.0149(5) Å]. In this case, however, the percentage differ- dition, {Me2MS[2,(4),6-Me3C6H2]}n (M = Al, Ga, In) all
ence in the Tl–E bond length (7%) is not great as that found show tetrameric structures, while M = Tl is polymeric. This
for the corresponding bond length in 3 (10%), which sug- demonstrates that the degree of oligomerization in the
gests that a stronger secondary interaction exists and that [Me2MERЈ]n species is affected not only by the choice of
6 is a more tightly bonded polymer. This is presumably a chalcogen (i.e. S/Se vs. O) but also by the triel metal atom
result of the larger atomic radius of Se versus S. As in 3, (i.e. Tl vs. Al/Ga/In).
the sum of the C1–Tl1–C2 [158.0(2)°], C1–Tl1–E1
[97.17(14)°], and C2–Tl1–E1 [101.40(15)°] bond angles is
Conclusions
approximately 357°, which gives a distorted T-shaped C2Se
bonding environment at Tl with a weak intermolecular
Tl···Se interaction.
Despite the large number of structural studies of dior-
gano group 13 chalcogenolates, this work represents the
first systematic study of diorganothallium thiolate and sele-
nolate analogues, and the first structurally characterized ex-
amples of the diorganothallium selenolates. The observed
solid-state structures of 1–6 suggest that the degree of oligo-
merization of [Me2TlERЈ]n (E = S, Se) may be varied upon
altering the steric bulk of the RЈ ligand. However, similar
structures are observed when E = S or Se for a given RЈ
group. A comparison of these structures to previously re-
ported [Me2TlORЈ]n solid-state structures further demon-
strated that the degree of oligomerization in the
[Me2MERЈ]n species may be affected by the choice of chal-
cogen (i.e. S/Se vs. O). A comparison between compounds
1–6 and the corresponding [Me2MSRЈ]n (M = Al, Ga, In)
analogues demonstrated that the observed structures are
also affected by the triel metal atom (i.e. Tl vs. Al/Ga/In).
These findings are important in understanding the factors
that govern oligomerization (i.e. ring size) and polymeriza-
tion in diorganotriel chalcogenolates.
Comparison to Previously Reported [RMERЈ]n Structures
The Tl–C bond lengths of 3–6 are within the range of
those reported for the [Me2TlERЈ]n (E = O, S) compounds
[2.05(4)–2.20(7) Å].[13,19,20] The CMe–Tl–CMe bond angles in
1 [163.5(9)°][13] and 4 [164.3(3)°] are similar to those ob-
served in the dimeric [Me2TlORЈ]2 complexes [156.9(2)–
171.9(2)°].[12] This results in a distorted see-saw type of ge-
ometry at Tl, despite the absence of a valence lone pair of
electrons. Furthermore, the CMe–Tl–CMe bond angles in 3–
6 are approximately 14 to 26° greater than the CMe–In–CMe
bond angles in the corresponding indium analogues.[11]
The majority of the previously reported [R2MERЈ]n (M
= Al, Ga, In; E = O, S, Se, Te) compounds exhibit dimeric
(n = 2) structures in the solid-state.[7] Other oligomers typi-
cally contain methyl groups on the group 13 metal (R =
Me), and have sulfur or selenium as the chalcogen (E = S,
Se) (Table 2).[9,10] Our structural and computational studies
of the indium complexes [R2InERЈ]n (E = O, S, Se) have
shown that the nature of the chalcogen, as well as the steric
properties of the R and RЈ groups, are important in de-
termining the degree of oligomerization in these com-
pounds.[11] The compounds that have E = O are dimeric
with strong intermolecular In···O bonds, unless RЈ is suffi-
ciently bulky (i.e. RЈ = 2,4,6-tBu3C6H2) to preclude dimer-
ization in which case a monomeric structure is observed.
Experimental Section
General Remarks: The solution 1H and 13C{1H} NMR spectra were
recorded at 23 °C with either a JEOL GMX 270 MHz + spectrome-
ter (270 and 67.9 MHz, respectively) or a Varian Mercury 200 MHz
+ spectrometer (200 and 50 MHz, respectively), and the chemical
shifts are calibrated to the residual solvent signal. The FTIR spec-
tra were recorded as Nujol mulls with NaCl plates with a Mattson
Alternatively, [Me2InERЈ]n (E = S, Se) compounds exhibit Genesis II FTIR spectrometer in the range of 4000 to 400 cm–1.
The FT-Raman spectra were recorded with a Thermo Nicolet
NXR 9600 Series FT-Raman spectrometer in the range of 3900 to
70 cm–1. The melting points were recorded with an Electrothermal
MEL-TEMP melting point apparatus and are uncorrected. The el-
emental analyses were performed by Chemisar Laboratories Inc.,
Guelph, Ontario. 2,6-Dimethylbenzenethiol (95%), benzeneselenol
(97%), mesitylmagnesium bromide (1.0 m in diethyl ether),
1-bromo-2,4,6-tri-tert-butylbenzene (99%), selenium powder
(–100 mesh, 99.5+%), butyllithium (1.6 m in hexanes), lithium alu-
minum hydride powder (95%), methyllithium (1.6 m in diether
dimeric, trimeric, tetrameric, polymeric, and weakly associ-
ated polymeric structures, which depends on the nature of
the RЈ group.
A comparison between the [Me2InERЈ]n and [Me2-
TlERЈ]n compounds (Table 2) shows that they have similar
structures and degrees of oligomerization for most of the
combinations of E and RЈ, with the exception of E = S, RЈ
= C6H5 and E = S, RЈ = 2,(4),6-Me3C6H2. If these –SRЈ
analogues are specifically considered, we see that
[Me2MSC6H5]n (M = Al, In) both exhibit similar polymeric ether), thallium(I) iodide (99.999%), iodomethane (99.5%), and
Table 2. The degree of oligomerization of the [Me2MERЈ]n (M = Al, Ga, In, Tl; E = O, S, Se) species [E (n)].
RЈ
Al
Ga
In
Tl
C6H5
2,(4),6-Me3C6H2
2,4,6-tBu3C6H2
S (ϱ)[a]
S (4)[e]
–
–
O (2),[b] S (ϱ),[b] Se (2)[b]
O (2),[b] S (4),[f] Se (ϱ)[b]
O (1),[b] S (1/ϱ),[b] Se (1/ϱ)[b]
O (2),[c] S (2),[d] Se (2)[d]
O (2),[c] S (ϱ),[d] Se (ϱ)[d]
O (1),[c] S (1/ϱ),[d] Se (1/ϱ)[d]
S (4)[e]
–
[a] Ref.[10] [b] Ref.[11] [c] Ref.[12] [d] This work. [e] Ref.[9b] [f] Ref.[9a] (1/ϱ) represents a weakly associated polymer.
Eur. J. Inorg. Chem. 2011, 5430–5436
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G. G. Briand et al.
FULL PAPER
sulfur powder (99.98%) were purchased from the Aldrich Chemical
Co. Toluene and tetrahydrofuran were dried by means of an
MBraun SPS column solvent purification system. All of the reac-
tions were performed under an atmosphere of inert dinitrogen by
using the standard Schlenk technique. 2,4,6-Trimethylbenzenesele-
nol, 2,4,6-tri-tert-butylbenzenethiol, and 2,4,6-tri-tert-butylben-
zeneselenol were prepared by the literature methods.[11,21] Me3Tl
was prepared by a modified literature procedure as indicated be-
low.[22,23]
([D8]THF): δ = 18.0 [d, 1JTl-13C = 2648 Hz, Me2TlS(2,6-Me2C6H3)],
23.5 [s, Me2TlS(2,6-Me2C6H3)], 122.4 [s, Me2TlS(2,6-Me2C6H3)],
126.1 [s, Me2TlS(2,6-Me2C6H3)], 140.9 [s, Me2TlS(2,6-Me2C6H3)],
142.4 [s, Me2TlS(2,6-Me2C6H3)] ppm.
[Me2TlS(2,4,6-tBu3C6H2)]ϱ (3): 2,4,6-tBu3C6H2SH (0.223 g,
0.802 mmol) was added to
a solution of TlMe3 (0.200 g,
0.802 mmol) in toluene (8 mL). The solution was stirred at room
temperature for 1 h, filtered and concentrated to 6 mL. The solu-
tion was allowed to sit at 4 °C for 1 d and filtered to yield 3 as
colorless crystals (0.328 g, 0.641 mmol, 80%). C20H35STl (511.93):
calcd. C 46.92, H 6.89, N 0.00; found C 47.25, H 7.08, N Ͻ 0.10;
Caution: Thallium is a cumulative poison that may be absorbed
through the skin. All compounds must be handled with extreme
care.
m.p. 329 °C. FTIR: ν = 646 (w), 723 (w), 754 (m), 779 (s), 876 (m),
˜
920 (vw), 1022 (w), 1038 (m), 1095 (w), 1163 (w), 1213 (m), 1238
(m), 1259 (w), 1281 (vw), 1358 (m), 1406 (m), 1591 (m), 2305 (vw),
2370 (vw) cm–1. FT-Raman: 143 (s), 171 (s), 256 (w), 333 (vw), 460
[vs, νsym(Me–Tl–Me)], 518 (vw), 566 (w), 611 (w), 779 (vw), 823
(w), 927 (vw), 1039 (m), 1129 (w), 1164 (m), 1185 (vw), 1282 (vw),
1381 (vw), 1448 (w), 1591 (m), 2701 (vw), 2913 (s), 2963 (s), 2996
(w), 3026 (w), 3105 (vw) cm–1. 1H NMR ([D8]thf): δ = 0.89 [d,
2JTl-H = 356 Hz, 6 H, Me2TlS(2,4,6-tBu3C6H2)], 1.63 [s, 9 H,
Me2TlS(2,4,6-tBu3C6H2)], 1.96 [s, 18 H, Me2TlS(2,4,6-tBu3C6H2)],
7.62 [s, 2 H, Me2TlS(2,4,6-tBu3C6H2)] ppm. 13C{1H} NMR
([D8]thf): δ = 19.3 [d, 1JTl-13C = 2225 Hz, Me2TlS(2,4,6-tBu3C6H2)],
31.4 [s, Me2TlS(2,4,6-tBu3C6H2)], 31.7 [s, Me2TlS(2,4,6-
tBu3C6H2)], 34.3 [s, Me2TlS(2,4,6-tBu3C6H2)], 37.4 [s, Me2TlS-
(2,4,6-tBu3C6H2)], 37.9 [s, Me2TlS(2,4,6-tBu3C6H2)], 120.2 [s,
Me2TlS(2,4,6-tBu3C6H2)], 114.1 [s, Me2TlS(2,4,6-tBu3C6H2)],
152.2 [s, Me2TlS(2,4,6-tBu3C6H2)] ppm.
Me3Tl: TlI (9.1 g, 27 mmol) was added to a solution of MeI (4.6 g,
32 mmol) in diethyl ether (30 mL) and the stirred suspension was
cooled to –100 °C. Methyllithium (1.6 m in diethyl ether, 38 mL,
61 mmol) was added dropwise over a 15 min period. The cold bath
was then removed and the reaction mixture was warmed to 23 °C.
After stirring for 18 h, the solvent was removed in vacuo. The crude
product was gradually heated to 88 °C (≈ 1 °C/min) under dynamic
vacuum and the colorless crystals of Me3Tl were collected by frac-
tional sublimation with an inline trap held at –30 °C (4.1 g,
1
2
16 mmol, 61%). H NMR ([D8]thf): δ = 0.26 [d, JTl-H = 266 Hz,
9 H, Me3Tl] ppm.
Caution: Me3Tl detonates above approximately 90 °C,[22] therefore
the sublimation temperature must be monitored closely.
[Me2TlS(C6H5)]2 (1): C6H5SH (0.110 g, 1.00 mmol) was added to
a solution of TlMe3 (0.250 g, 1.00 mmol) in toluene (8 mL). The
solution was stirred at room temperature for 1 h and filtered to
yield 1 (0.165 g, 0.479 mmol, 48%). C16H22S2Tl2 (687.21): calcd. C
27.96, H 3.23, N 0.00; found C 28.13, H 3.18, N Ͻ 0.10; m.p. 194–
[Me2TlSe(C6H5)]2 (4): C6H5SeH (0.126 g, 0.802 mmol) was added
to a solution of TlMe3 (0.200 g, 0.802 mmol) in thf (8 mL). The
solution was stirred at room temperature for 1 h and filtered to
remove the precipitated product. The solution was then concen-
trated to 4 mL and was allowed to sit at 4 °C for 1 d. The colorless
crystals of 4 were then collected by filtration (0.114 g, 0.292 mmol,
36%). C16H22Se2Tl2 (781.01): calcd. C 24.61, H 2.84, N 0.00; found
196 °C. FTIR: ν = 698 (s), 738 (vs), 791 (vs), 908 (w), 980 (w), 1024
˜
(m), 1066 (m), 1082 (m), 1153 (w), 1261 (w), 1300 (w), 1400 (w),
1435 (s), 1568 (m), 1581 (m), 1643 (vw), 1714 (vw), 1745 (vw), 1807
(vw), 1871 (w), 1946 (w), 2308 (w), 3008 (m), 3055 (m) cm–1. FT-
Raman: 117 (m), 166 (m), 323 (w), 310 (vw), 419 (vw), 474 [vs,
νsym(Me–Tl–Me)], 530 (w), 616 (vw), 697 (w), 791 (vw), 1002 (m),
1023 (m), 1082 (m), 1117 (vw), 1155 (w), 1171 (m), 1436 (vw), 1581
(w), 2917 (m), 3010 (w), 3058 (m), 3134 (vw) cm–1. 1H NMR
([D6]dmso): δ = 1.01 [d, 2JTl-H = 372 Hz, 6 H, Me2TlS(C6H5)], 7.14
[m, 1 H, Me2TlS(C6H5)], 7.32 [m, 2 H, Me2TlS(C6H5)], 7.51–7.56
C 24.26, H 3.16, N Ͻ 0.10; m.p. 207 °C. FTIR: ν = 696 (s), 733
˜
(vs), 785 (vs), 1020 (m), 1065 (m), 1151 (m), 1261 (w), 1296 (w),
1396 (w), 1433 (vs), 1572 (m), 1745 (vw), 1871 (vw), 1948 (w), 2301
(vw), 3006 (m), 3055 (w) cm–1. FT-Raman: 144 (s), 199 (m), 253
(w), 307 (vw), 469 [vs, νsym(Me–Tl–Me)], 526 (w), 615 (w), 668 (w),
788 (w), 1002 (s), 1020 (w), 1070 (m), 1153 (w), 1167 (w), 1575 (w),
2913 (m), 3007 (w), 3057 (m) cm–1. 1H NMR (CDCl3): δ = 1.13 [d,
[m, 2 H, Me2TlS(C6H5)] ppm. 13C{1H} NMR ([D6]DMSO):
1
δ
=
20.2 [d, JTl-13C
=
2913 Hz, Me2TlS(C6H5)], 122.4 [s,
2JTl-H
= 346 Hz, 6 H, Me2TlSe(C6H5)], 7.11 [m, 3 H,
Me2TlS(C6H5)], 127.9 [s, Me2TlS(C6H5)], 134.2 [s, Me2TlS(C6H5)],
146.2 [s, Me2TlS(C6H5)] ppm.
Me2TlSe(C6H5)], 7.35 [m, 2 H, Me2TlSe(C6H5)] ppm. 13C{1H}
1
NMR (CDCl3): δ = 40.6 [d, JTl-13C = 3434 Hz, Me2TlSe(C6H5)],
[Me2TlS(2,6-Me2C6H3)]ϱ
(2):
2,6-Me2C6H3SH
(0.111 g,
125.4 [s, Me2TlS(C6H5)], 128.6 [s, Me2TlS(C6H5)], 135.6 [s,
Me2TlS(C6H5)] ppm.
0.802 mmol) was added to
a
solution of TlMe3 (0.200 g,
0.802 mmol) in toluene (8 mL). The solution was stirred at room
temperature for 1 h, filtered, and concentrated to 3 mL. The re-
sulting colorless product was then dissolved in thf (4 mL). The
solution was allowed to sit at 4 °C for 1 d and filtered to yield 2 as
[Me2TlSe(2,4,6-Me3C6H2)]ϱ (5): 2,4,6-Me3C6H2SeH (0.159 g,
0.802 mmol) was added to
a solution of TlMe3 (0.200 g,
0.802 mmol) in thf (8 mL). The solution was stirred at room tem-
colorless crystals (0.127 g, 0.341 mmol, 43%). C10H15STl (371.66): perature for 1 h, filtered, and concentrated to 4 mL. The solution
calcd. C 32.32, H 4.07, N 0.00; found C 32.46, H 4.25, N Ͻ 0.10;
m.p. 205 °C. FTIR: ν = 588 (w), 656 (vw), 721 (w), 760 (m), 903
was allowed to sit at 4 °C for 1 d and filtered to yield 5 as colorless
needle crystals (0.096 g, 0.222 mmol, 28%). C11H17SeTl (432.59):
˜
(w), 982 (vw), 1014 (vw), 1051 (w), 1080 (vw), 1163 (vw), 1246 (w), calcd. C 30.55, H 3.96, N 0.00; found C 30.77, H 3.98, N Ͻ 0.10;
1259 (w), 1321 (vw), 1539 (w), 1579 (w) cm–1. FT-Raman: 116 (s), m.p. 197 °C. FTIR: ν = 706 (w), 723 (m), 789 (s), 850 (s), 879 (w),
˜
236 (w), 422 (vw), 461 [vs, νsym(Me–Tl–Me)], 518 (w), 589 (w), 767
951 (w), 1020 (s), 1093 (w), 1159 (m), 1261 (m), 1296 (m), 1599
(m), 1056 (m), 1116 (vw), 1166 (m), 1248 (m), 1376 (vw), 1401 (vw), (w), 1726 (vw), 1759 (vw), 2305 (w), 2357 (vw), 2725 (w) cm–1. FT-
1429 (vw), 1458 (vw), 1583 (m), 2840 (vw), 2915 (m), 3008 (w), Raman: 115 (vs), 143 (s), 330 (w), 464 [vs, νsym(Me–Tl–Me)], 518
1
2
3052 (w) cm–1. H NMR ([D8]thf): δ = 0.69 [d, JTl-H = 372 Hz, 6
(w), 540 (w), 779 (vw), 1021 (w), 1094 (vw), 1165 (m), 1294 (m),
1
H, Me2TlS(2,6-Me2C6H3)], 2.43 [s, 6 H, Me2TlS(2,6-Me2C6H3)],
1378 (w), 1599 (m), 2911 (s), 3002 (m) cm–1. H NMR ([D8]thf): δ
6.67 [t, 3JH-H = 7.0 Hz, 1 H, Me2TlS(2,6-Me2C6H3)], 6.93 [3JH-H
=
= 0.78 [d, 2JTl-H = 368 Hz, 6 H, Me2TlSe(2,4,6-Me3C6H2)], 2.25 [s,
7.0 Hz,
2
H, Me2TlS(2,6-Me2C6H3)] ppm. 13C{1H} NMR 3 H, Me2TlSe(2,4,6-Me3C6H2)], 2.46 [s, 6 H, Me2TlSe(2,4,6-
5434
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© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2011, 5430–5436

Dimethylthallium(III) S and Se Rings and Polymers
Table 3. Crystallographic data for 3–6.
3
4
5
6
Empirical formula
Fw
Crystal system
Space group
a [Å]
b [Å]
c [Å]
α [°]
C20H35STl
511.91
C16H22Se2Tl2
781.00
orthorhombic
Pbca
11.9139(17)
7.5855(11)
21.023(3)
90
C11H17SeTl
432.58
orthorhombic
Pca2(1)
22.887(6)
7.0094(17)
7.6804(19)
90
C20H35SeTl
558.81
monoclinic
P2(1)/c
13.1663(13)
9.1552(9)
17.2455(16)
90
monoclinic
P2(1)/c
13.2032(17)
9.2144(12)
17.350(2)
90
β [°]
92.5450(10)
90
2076.7(3)
4
90
90
1899.9(5)
4
90
90
1232.1(5)
4
92.924(2)
90
2108.0(5)
4
γ [°]
V [Å3]
Z
F(000)
1008
1.637
7.875
173(1)
1392
2.730
20.763
198(1)
792
2.332
16.020
173(1)
1080
1.761
9.386
173(1)
ρcalcd (gcm–3)
μ [mm–1]
T [K]
Reflections collected
Independent reflections (Rint
13580
4642 (0.0538)
0.0303
0.0850
1.863
10950
7935
13891
4685 (0.0649)
0.0306
0.0827
0.895
)
2139 (0.1049)
0.0619
0.1735
3.750
2644 (0.0763)
0.0347
0.0761
3.704
[a]
R1
wR2
[b]
Largest diff. peak [eÅ–3]
Largest diff. hole [eÅ–3]
–1.456
–3.292
–1.197
–2.771
2
2
2 2
[a] R1 = [Σ||Fo| – |Fc||]/[Σ|Fo|] for [Fo Ͼ 2σ(Fo2)]. [b] wR2 = {[Σw(Fo – Fc ) ]/[Σw(Fo4)]}1/2.
Me3C6H2)], 6.84 [s, 2 H, Me2TlSe(2,4,6-Me3C6H2)] ppm. 13C{1H}
NMR ([D8]thf): δ = 18.0 [d, JTl-13C = 2628 Hz, Me2TlSe(2,4,6-
Me3C6H2)], 20.2 [s, Me2TlSe(2,4,6-Me3C6H2)], 37.4 [s,
(SAINT)[24] and corrected for absorption (SADABS).[25] The struc-
tures were solved by direct methods and were refined by full-matrix
least-squares on F2 (SHELXTL).[26] All of the non-hydrogen atoms
1
Me2TlSe(2,4,6-Me3C6H2)], 99.9 [s, Me2TlSe(2,4,6-Me3C6H2)], were refined by using anisotropic displacement parameters. The hy-
126.9 [s, Me2TlSe(2,4,6-Me3C6H2)], 133.0 [s, Me2TlSe(2,4,6-
Me3C6H2)], 142.1 [s, Me2TlSe(2,4,6-Me3C6H2)] ppm.
drogen atoms were included in the calculated positions and were
refined by using a riding model.
The X-ray crystallographic data for 3–6 is presented in Table 3.
CCDC-832989 (for 3), -832993 (for 4), -832994 (for 5) and -832995
(for 6) contain the supplementary crystalloraphic data for this
paper. These data can be obtained free of charge from The Cam-
bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
[Me2TlSe(2,4,6-tBu3C6H2)]ϱ (6): 2,4,6-tBu3C6H2SeH (0.260 g,
0.802 mmol) was added to
a solution of TlMe3 (0.200 g,
0.802 mmol) in toluene (8 mL). The solution was stirred at room
temperature for 1 h, filtered, and concentrated to 6 mL. The solu-
tion was allowed to sit at 4 °C for 1 d and filtered to yield 6 as
colorless crystals (0.341 g, 0.610 mmol, 76%). C20H35SeTl (558.83):
calcd. C 42.99, H 6.31, N 0.00; found C 43.27, H 6.65, N Ͻ 0.2;
m.p. 215 °C. FTIR: ν = 644 (w), 727 (w), 744 (m), 777 (s), 876 (m),
˜
Acknowledgments
899 (w), 922 (w), 1016 (m), 1093 (vw), 1126 (vw), 1161 (w), 1184
(m), 1213 (m), 1236 (m), 1254 (w), 1279 (w), 1358 (s), 1587 (m),
1755 (vw), 2303 (w), 2729 (vw), 3103 (vw) cm–1. FT-Raman: 136
(s), 167 (s), 256 (w), 457 [vs, νsym(Me–Tl–Me)], 514 (w), 566 (m),
780 (w), 822 (m), 927 (w), 1016 (m), 1128 (w),1163 (m), 1199 (vw),
1279 (vw), 1355 (vw), 1446 (m), 1588 (m), 2701 (vw), 2912 (s), 2962
(s), 3025 (w) cm–1. 1H NMR ([D8]thf): δ = 0.39 [d, 2JTl-H = 354 Hz,
6 H, Me2TlSe(2,4,6-tBu3C6H2)], 1.13 [s, 9 H, Me2TlSe(2,4,6-
tBu3C6H2)], 1.45 [s, 18 H, Me2TlSe(2,4,6-tBu3C6H2)], 7.11 [m, 2 H,
We thank Dan Durant for assistance in collecting solution NMR
spectroscopic data, the Natural Sciences and Engineering Research
Council of Canada, the New Brunswick Innovation Foundation,
the Canadian Foundation for Innovation, and Mount Allison Uni-
versity for financial support.
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1
[d, JTl-13C
= 2294 Hz, Me2TlSe(2,4,6-tBu3C6H2)], 31.4 [s,
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139.9 [s, Me2TlSe(2,4,6-tBu3C6H2)], 143.8 [s, Me2TlSe(2,4,6-
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from the reaction mixtures as indicated above. The single-crystals
were coated with Paratone-N oil, mounted by using a 20 micron
cryo-loop, and frozen in the cold nitrogen stream of the goniome-
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www.eurjic.org
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Received: July 25, 2011
Published Online: November 11, 2011
5436
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Eur. J. Inorg. Chem. 2011, 5430–5436