A Structural Investigation of Dimethylthallium(III) Thiolate and Selenolate Rings and Polymers

Abstract

The effects of increased steric bulk in dimethylthallium(III) chalcogenolates on oligomerization was examined. The facile reaction of Me3Tl with a series of benzenethiols and ‐selenols in toluene or thf resulted in the formation of [Me2TlS(2,6‐Me2C6H3)]∞ (2), [Me2TlS(2,4,6‐tBu3C6H2)]∞ (3), [Me2TlSe(C6H5)]2 (4), [Me2TlSe(2,4,6‐Me3C6H2)]∞ (5), and [Me2TlSe(2,4,6‐tBu3C6H2)]∞ (6). The solid‐state structure of 4 is dimeric with short intermolecular Tl···Se interactions, which yields an asymmetric Tl2Se2 core and a distorted tetrahedral C2Se2 bonding environment for the thallium. The increase in the steric bulk of the chalcogenolate ligand in compounds 2 and 5 results in the formation of polymeric structures with μ‐E[2,(4),6‐Me3C6H2] (E = S, Se) groups and distorted tetrahedral C2E2 bonding environments for the thallium. A further increase in the steric bulk of the phenylchalcogenolate resulted in the formation of chains of weakly coordinated 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 structurally characterized examples of R2TlSeR′ species. A comparison 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 [Me2MSR′]n (M = Tl) versus the analogous (M = Al, Ga, and In) species. These findings areimportant in understanding the factors that govern oligomerization (i.e. ring size) and polymerization of diorganotriel chalcogenolates.

Synthesis and crystal structure of bis(μ-2-methylbenzenethiolato-κ2S:S)bis[methyl(2-methylbenzenethiolato-κS)indium(III)]

“…2). Such contacts are common for indium and other heavy main group metal chalcogenolates due to their large metal radii and potential for high coordination numbers (Briand et al, 2010(Briand et al, , 2011(Briand et al, , 2012Appleton et al, 2011). This leads to the formation of insoluble materials for iBuIn(SPh) 2 (Nomura et al, 1989).…”

Boron, aluminium, gallium, indium and thallium

“…Structural investigations of these polymorphs in the solid state reveal unexpected room-temperature crystal-to-crystal phase transition and the presence of significant TlÁ Á ÁTl contacts. 315 The facile reaction Me 3 Tl with phenols 316 benzenethiols and selenols 317 ] have been reported. The effects of increased steric bulk in dimethylthallium(III) chalcogenolates on oligomerisation were examined and an insight into the factors that govern oligomerisation (i.e.…”