Synthesis and characterization of pentamethylcyclopentadienylrhodium(III) and -iridium(III) complexes with 1,2-benzenedithiolate · [(Cp ∗Rh) 2(μ( S)-1,2-C 6H 4S 2- S, S′) 2], [(Cp ∗Rh) 2(μ( S)-1,2-C 6H 4S 2- S,S′)(μ( S)-1,2-C 6H 4S(SO 2)- S,S′)] and [(Cp ∗Ir)(1,2-C 6H 4S 2- S,S′)] ( [formula omitted]) Professor Peter M. Maitlis on the occasion of his 65th birthday and in recognition of his

Abstract

A reaction of the triple cubane-type organometallic polyoxomolybdate cluster, [(Cp ∗Rh) 4Mo 4O 16]·2H 2O( 1 · 2H 2O), with 1,2-benzenedithiol gives a 1,2-benzenedithiolate-bridged dinuclear complex, [(Cp ∗Rh) 2(μ( S)-1,2-C 6H 4S 2- S,S′) 2] ( 2), and another dinuclear complex, [(Cp ∗Rh) 2(μ( S)-1,2-C 6H 4S 2- S,S′)(μ( S)-1,2-C 6H 4S(SO 2)- S,S′)] ( 3), both of which are characterized by the single-crystal X-ray diffraction method. The former complex, 2,is also obtained from a reaction of [(Cp ∗RhCl) 2(μ-Cl 2] with 1,2-benzenedithiol in the presence of NaOCH 3, and the latter, 3, from oxygenation of 2 with t-BuOOH. The 1H NMR study in CD 2Cl 2 indicates that complex 2 changes gradually to a coordinatively unsaturated mononuclear complex, [(Cp ∗Rh(1,2-C 6H 4S 2- S,S′)] ( 4). An analogous mononuclear iridium(III) complex, [Cp ∗Ir(1,2-C 6H 4S 2- S,S′)] ( 5), is also prepared and characterized by X-ray structural analysis.