C4-ring ligand-transfer reactions: applications to cluster chemistry. Crystal structures of [Ru5C(CO)13(η-C4Ph4)] and [Ru6C(CO)15(η-C4Ph4)

Abstract

Redox-mediated ligand-transfer reactions between the cationic complex [Pd(η-C4Ph4)(Me2CO)2]2+ and the dianionic clusters, [Ru5C(CO)14]2– and [Ru6C(CO)16]2– afforded [Ru5C(CO)13(η-C4Ph4)]1 and [Ru6C(CO)15(η-C4Ph4)]2, respectively. The new clusters 1 and 2 have been characterised by spectroscopic techniques in solution and in the solid-state by single-crystal X-ray diffraction. In 1 the ring is co-ordinated to a basal ruthenium atom of the square-pyramidal cluster framework, while in 2 the octahedral metal core of the parent complex has opened slightly through the elongation of one Ru–Ru bond. The reasons for this structureal change have been analysed using extended-Huckel molecular-orbital calculations.