Dicoordinate copper(I) silanechalcogenolates.
2006
The copper silanechalcogenolates tBu3PCuESiPh3 (1, E = O; 2, E = S; 3, E = Se) were prepared from the reaction of [tBu3PCu(CH3CN)3]BF4 with [Ph3SiELi(THF)2]2 in acetonitrile. The compounds were obtained as colorless, crystalline, but thermally labile solids. X-ray crystallography shows that complexes 1−3 are monomeric in the solid state with no Cu···Cu interactions. The Cu atoms have either a linear or a near-linear coordination geometry in all three complexes. Interestingly, the O atom in complex 1 is also linear, which is in contrast to the highly bent S (2) and Se analogues (3). Density functional theory calculations suggest that both the linear geometry of 1 and an associated extremely short Cu−O distance [1.769(4) A] are not the result of π delocalization but are the result of a fine balance of electrostatic interaction and Pauli repulsion.
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