Rh2(PMe3)2(CO)2Cl2 (2) has been found to catalyze the decarbonylation of aldehydes to give the corresponding alkanes. Reaction rates are comparable to those of the most active nonradical systems previously reported. A mechanistic study indicates that the turnover-limiting reaction step includes addition of the aldehydic C-H bond to an intact molecule of 2; ligand dissociation or cleavage of the chloride bridge does not occur prior to the C-H addition step. This conclusion is based on kinetic studies (d[R′H]/dr = kobs [R′CHO]; R′ = n-C11H23; kobs = 2.2 × 10-4 M-1 s-1; ΔS‡ = -26 eu) and the observation of a significant kinetic isotope effect (kRCHO/RCDO > 1.8).
ASJC Scopus subject areas
- Colloid and Surface Chemistry