Oxidative addition of C-H bonds to RhCl(PMe3)3: relevant to the catalytic transformation of hydrocarbons.
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).
Choi
Jun-Chul
JC
National Institute of Advanced Industrial Science and Technology (AIST), Higashi, AIST Central 5, Tsukuba 305-8565, Japan.
Sakakura
Toshiyasu
T