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Methyl group influence on the formation of CuI complexes with thio-pyridine ligands

Caradoc-Davies, P.L. and Hanton, L.R. and Hodgkiss, J.M. and Spicer, M.D. (2002) Methyl group influence on the formation of CuI complexes with thio-pyridine ligands. Journal of the Chemical Society, Dalton Transactions, 2002 (8). pp. 1581-1585. ISSN 0300-9246

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In order to investigate the effect of methyl group substitution adjacent to a pyridyl N donor, three ligands were synthesised and complexed with CuI in a 1:2 ratio. The crystal structures of three CuI complexes were determined. The dimethylated ligand bis(6-methyl-2-pyridylmethyl)sulfide (L-1) gave rise to a tetranuclear complex with two Cu2I2 bridges in which the Cu centres were four-coordinate. The asymmetric ligand 2-(6-methylpyridyl) methyl(2-pyridyl) methylsulfide (L-2) gave a tetranuclear complex which contained two parallel Cu2I2 bridges. In each Cu2I2 bridge, one Cu centre was three- and the other four-coordinate. In contrast, the ligand bis(2-pyridylmethyl) sulfide (L-3), with no Me substitution, gave rise to a one-dimensional coordination polymer with CuI chains. It was found that the differences in the complexes were a result of both the electronic and steric effects arising from the Me substitution of the pyridine donors and that no one effect completely dominated.