title: Oxidative addition of C-H bonds to RhCl(PMe3)3: relevant to the catalytic transformation of hydrocarbons.
abstract: RhCl(PMe3)3 (1) reacts with benzene under irradiation to give the oxidative addition product, Rh(C6H5)(H)Cl(PMe3)3 (2). The reaction is promoted under CO2 atmosphere. The structure of 2 was fully characterized by X-ray crystallography as well as NMR, IR, and elemental analysis. The adduct (2) is unstable in solution even at room temperature to regenerate benzene and 1. The thermolysis of 2 under a CO atmosphere produces benzaldehyde along with the reductive elimination product, benzene. On the other hand, the prolonged photoreaction of 1 with benzene under CO2 resulted in the activation of the C-H bond and CO2 to yield Rh(C6H5)(eta2-CO3)(PMe3)3 (3).
authors.affiliation: National Institute of Advanced Industrial Science and Technology (AIST), Higashi, AIST Central 5, Tsukuba 305-8565, Japan.
authors.forename: Jun-Chul
authors.initials: JC
authors.lastname: Choi
authors.forename: Toshiyasu
authors.initials: T
authors.lastname: Sakakura