Trialkylphosphine-stabilized copper(I) phenylchalcogenolate complexes - Crystal structures and copper-chalcogenolate bonding

Article abstract of DOI:10.1021/ic102249g

A series of trialkylphosphine-stabilized copper(I) phenylchalcogenolate complexes [(R₃P)_m(CuEPh)_n] (R = Me, Et, ⁱPr, ^tBu; E = S, Se, Te) has been prepared and structurally characterized by X-ray diffraction. Structures were found to be mono-, di-, tri-, tetra-, hexa-, hepta-, or decanuclear, depending mainly on size and amount of phosphine ligand. Several structural details were observed, including unusually long Cu-E bonds or secondary Cu-E connections, μ4-bridging, and planar bridging chalcogenolate ligands. Relatively rigid Cu-E-C angles were found to be of significant influence on the flexible molecular structures, especially for bridging chalcogenolate ligands, since in these cases a correlation results between the Cu-E-Cu angles and the inclination of the E-C bonds to their Cu-E-Cu planes. We further address some of these phenomena by means of density functional computations.