Iridium Dimer Anion-Mediated C≡C Triple Bond Cleavage and Successive Dehydrogenation of Acetylene in the Gas Phase.

Abstract

The reactions of the iridium dimer anion [Ir2]- with acetylene have been studied by mass spectrometry in the gas phase, which indicate that the [Ir2]- anion can consecutively react with C2H2 molecules to form the [Ir2C2x]- (x = 1, 2) and [Ir2C2yH2]- (y = 3-5) anions as major products with the successive release of H2 molecules at room temperature. The reactions are confirmed by the reactions of the mass-selected product [Ir2C2]- anion with C2H2 to produce [Ir2C4]- and [Ir2C2yH2]- (y = 3-5). Photoelectron spectra and quantum chemistry calculations confirm that the [Ir2C2x]- (x = 1, 2) product anions possess cyclic [Ir(μ-C)2Ir]- and [Ir(μ-C)(μ-C3)Ir]- structures, implying that the robust C≡C triple bond of acetylene can be completely cleaved by the [Ir2]- anion.