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摘要
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)]8 (2), [Me2TlS(2,4,6-tBu3C6H2)]8 (3), [Me2TlSe(C6H5)]2 (4), [Me2TlSe(2,4,6-Me3C6H2)]8 (5), and [Me2TlSe(2,4,6-tBu3C6H2)]8 (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 (-)mu 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 TlE interactions in 3 (E = S) and 6 (E = Se). This work represents the first systematic study of diorganothallium thiolates and selenolates and compounds 46 represent the first structurally characterized examples of R2TlSeR' species. A comparison of the structures of [Me2TlS(C6H5)]2 (1) and 26 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.
- 出版日期2011-12
