Kinetics and mechanisms of homogeneous catalytic reactions: Part 15. Regio-specific hydroformylation of limonene catalysed by rhodium complexes of phosphine ligands

Limonene hydroformylation was studied in the presence of Rh-based catalytic systems, which were prepared in situ by addition of three equivalents of PPh3, one of 1,2-bis(diphenylphosphino)ethane (dppe), or one of 1,1,1-tris(diphenylphosphino)ethane (triphos) to Rh(CO)(2)(acac) (1). These systems were efficient precatalysts for the target reaction, generating limonenal regio-specifically under mild reaction conditions (80 A degrees C and 20 atm of syngas). The found activity order was: (1)/3 PPh3 > (1)/triphos > (1)/dppe. The active catalytic species are proposed to be square planar hydrido-carbonyl complexes containing two phosphorus atoms coordinated at the rhodium centre. A kinetic study of this reaction catalysed by (1)/3 PPh3, the most active catalytic system, allowed us to propose that the mechanism of hydroformylation of limonene is similar to those reported for other olefins using RhH(CO)(PPh3)(3) or Rh systems containing either dppe or triphos as precatalysts.