Transition metal activation and functionalization of carbon-hydrogen bonds. Progress report, December 1, 1992--November 30, 1993.

摘要

A method was developed for synthesizing a new complex for studying C-H activation, (HBPz*(sub 3))Rh(CNCH(sub 2)CMe(sub 3))(PhN=C=NCH(sub 2)CMe(sub 3)). This complex loses the carbodiimide ligand, thereby serving as a precursor for a 16-electron Rh(I) fragment which activates (via oxidative addition) a wide range of aromatic and aliphatic C-H bonds. Mechanism of activation of benzene by this fragment was studied. Reaction of (Tp'Rh(CNR)) fragment with aliphatic hydrocarbons was also studied. A study of C-H bond activation by the complex MnH(sub 3)(dmpe)(sub 2) was completed. Reactions of (Ru(dmpe)(sub 2)) with several small molecules were also investigated. Effects of fluorine substituents on aromatic ring on C-H activation were looked at. Studies of (eta)(sup 2)-arene coordination with ((C(sub 5)Me(sub 5))Rh(PMe(sub 3))) were completed; studies of reaction of this complex with 1,3-disubstituted benzenes are in progress.