Pentamethylcyclopentadienyl rhodium complexes

Abstract

We report syntheses and structures of pentamethylcyclopentadienyl (Cp∗) rhodium(III) and rhodium(I) complexes. Dicationic rhodium(III) complexes, [Cp∗Rh(bpy)(MeCN)](PF_6)_2 and [Cp∗Rh(vbpy)(MeCN)](PF_6)_2 (bpy = 2,2′-bipyridyl and vbpy = 4-vinyl-2,2′-bipyridyl), were prepared by treatment of [Cp∗Rh(MeCN)_3](PF_6)_2 with bpy and vbpy, respectively. The monocationic rhodium(III) complex, [Cp∗Rh(Me_4phen)Cl]Cl (Me_4phen = 3,4,7,8-tetramethyl-1,10-phenanthroline), was prepared by treatment of the chloride-bridged rhodium dimer, [Cp∗RhCl_2]_2, with Me_4phen. Two rhodium(I) complexes were synthesized via reduction of their rhodium(III) counterparts using two different methods: Cp∗Rh(bpy) was produced via a new route involving treatment of [Cp∗Rh(bpy)Cl]Cl with thallium formate in dry acetonitrile, whereas [Cp∗Rh(Me_4phen)Cl]Cl was reduced with Na(Hg) to give Cp∗Rh(Me_4phen). The colors of the Rh(I) complexes are attributable to relatively intense visible-region MLCT absorptions.

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