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A Structural Investigation of Dimethylthallium(III) Thiolate and Selenolate Rings and Polymers
Author(s) -
Briand Glen G.,
Decken Andreas,
Hunter Nicole M.,
Wright John A.,
Zhou Y.
Publication year - 2011
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201100773
Subject(s) - chemistry , steric effects , crystallography , intermolecular force , thallium , ligand (biochemistry) , monomer , chalcogen , stereochemistry , molecule , polymer , inorganic chemistry , organic chemistry , biochemistry , receptor
The effects of increased steric bulk in dimethylthallium(III) chalcogenolates on oligomerization was examined. The facile reaction of Me 3 Tl with a series of benzenethiols and ‐selenols in toluene or thf resulted in the formation of [Me 2 TlS(2,6‐Me 2 C 6 H 3 )] ∞ ( 2 ), [Me 2 TlS(2,4,6‐ t Bu 3 C 6 H 2 )] ∞ ( 3 ), [Me 2 TlSe(C 6 H 5 )] 2 ( 4 ), [Me 2 TlSe(2,4,6‐Me 3 C 6 H 2 )] ∞ ( 5 ), and [Me 2 TlSe(2,4,6‐ t Bu 3 C 6 H 2 )] ∞ ( 6 ). The solid‐state structure of 4 is dimeric with short intermolecular Tl ··· Se interactions, which yields an asymmetric Tl 2 Se 2 core and a distorted tetrahedral C 2 Se 2 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‐Me 3 C 6 H 2 ] (E = S, Se) groups and distorted tetrahedral C 2 E 2 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 R 2 TlSeR′ species. A comparison of the structures of [Me 2 TlS(C 6 H 5 )] 2 ( 1 ) and 2 – 6 with other group 13 analogue structures suggests that the degree of oligomerization differs for [Me 2 MSR′] 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.