Synthesis, Structure, and Reactivity of Iridacyclohexadienone and Iridaphenol Complexes¹

Abstract

Iridacyclohexadienone complexes, a new class of unsaturated six-membered metallacycles, have been synthesized, and their reactions with acids have been investigated. Treatment (“iridabenzene” 1) with nitrous oxide produces the iridacyclohexadienone which upon stirring in diethyl ether solution slowly isomerizes to (1,2,5-η-2,4-dimethylpenta-1,3-dien-5-oyl)Ir(PMe3)3 (3). Treatment of 2 with methyl trifluoromethanesulfonate leads to removal of the metal hydride and production In acetone solution, 4 forms an equilibrium mixture with a ring-contracted iridacyclopentadiene Treatment of 4 with trimethylphosphine generates the tetrakis(trimethylphosphine)iridacyclohexadienone Iridacyclohexadienone 2 reacts with trifluoromethanesulfonic acid to produce the iridacyclopentene In contrast, treatment of iridacyclohexadienones 4 and 6 with trifluoromethanesulfonic acid leads to protonation of oxygen and production of the corresponding “iridaphenols” 8 and 10. When 4 is treated with trifluoroacetic acid, an iridaphenol...