The competitive activation of C-H bonds of linear, cyclic, and branched hydrocarbons using the coordinatively unsaturated 16-electron [Tp'RhL] reactive fragment have been studied (Tp' = tris-(3,5d m ethyl pyrazolyl) borate; L = CNCH2CMe3). Activation of the hydrocarbons leads to the formation of Tp'Rh-(L)(R)(H) alkyl complexes, which were converted to the stable chlorides immediately following the activation of the bonds via photolysis of Tp'Rh(L)(PhN=C=NCH2CMe3) in the solvent mixture. The products were analyzed by H-1 NMR spectroscopy. The experiments described provide relative rates for the coordination of primary and secondary C-H bonds to the Rh metal center, indicating a 1.5x preference for the latter.