Journal of Physical Chemistry A, Vol.102, No.11, 1963-1964, 1998
Prediction of the reactive intermediates in alkane activation by tris(pyrazolyl borate)rhodium carbonyl
Two intermediates are observed in the time-resolved IR spectra of the photoinitiated alkane (RH) activation reaction of Tp*Rh(CO)(2) (Tp* = HB-(3,5-dimethylpyrazolyl). Density functional calculations suggest that the first observed intermediate is (eta(3)-Tp*)Rh(CO)...(RH) (RH weakly bound), which subsequently rearranges to (eta(2)-Tp*)Rh(CO)(RH) (RH strongly bound) before undergoing oxidative addition to the product (eta(3)-Tp*)-Rh(CO)(R)(H).
Keywords:FEMTOSECOND TRANSIENT ABSORPTION;EFFECTIVE CORE POTENTIALS;H BOND ACTIVATION;PHOTOGENERATED CR(CO)5(ROH);MOLECULAR CALCULATIONS;SPECTROSCOPY;CR(CO)6;PHOTODISSOCIATION;SOLVATION;IR