Fluorophosphine complexes of rhodium(I) and iridium(I): towards the design of systems with extended metal–metal interactions. The crystal structure of [{IrCl(PF3)2}2]

Abstract

A single-crystal X-ray structure determination of [{IrCl(PF₃)₂}₂](1)[monoclinic, P2₁/_n, a= 10.526(1), b= 10.346(2), c= 13.150(1)Å, β= 101.46(1)°, R= 0.0481] has confirmed the existence of dimeric molecules with short intra- and inter-molecular irdium–iridium contacts and infinite zigzag chains of iridium atoms. Detailed consideration of the structure allows conclusions to be drawn about the design of other fluorophosphineiridium(I) complexes with extended metal–metal interactions. These conclusions have been tested by syntheses of a variety of complexes of Rh^I and Ir^I containing the ligands PF₂(NMe₂), PF(O₂C₆H₄), and OC(NMePF₂)₂. The complex [{IrCl[OC(NMePF₂)₂]}₂] probably has a structure involving extended metal–metal interactions.