Syntheses and reactions of hydridorhodium(III) octaethylporphyrin and rhodium(II) octaethylporphyrin dimer

Abstract

Hydridorhodium(III) octaethylporphyrin, (OEP)Rh^III–H (1), was formed by the introduction of hydrogen gas into a methanol solution of (OEP)Rh^III–Cl or by the acidification of the (OEP)Rh^I anion in alcoholic solution. Complex (1) when degassed to liberate hydrogen or aerially oxidized in benzene gave a dimeric complex with Rh–Rh bonding which was formulated as [(OEP)Rh^II]₂(2). The reaction of (2) with alkyl halides, unactivated olefins, and acetylenes occurred smoothly to afford organorhodium(III)–OEP complexes (3)–(11).