title: Dialkylamino cyclopentadienyl ruthenium(ii) complex-catalyzed alpha-alkylation of arylacetonitriles with primary alcohols.
abstract: Aminocyclopentadienyl ruthenium complexes, [(eta(5)-C(5)H(4)NMe(2))Ru(PPh(3))(2)(CH(3)CN)](+)BF(4)(-) and [(eta(5)-C(5)H(4)NEt(2))Ru(PPh(3))(2)(CH(3)CN)](+)BF(4)(-), are moderately active catalysts for alpha-alkylation of arylacetonitriles with primary alcohols; on the other hand, the analogous unsubstituted cyclopentadienyl ruthenium complex [(eta(5)-C(5)H(5))Ru(PPh(3))(2)(CH(3)CN)](+)BF(4)(-) shows very low catalytic activity. On the basis of experimental results and theoretical calculations, rationalization for the much higher catalytic activity of the aminocyclopentadienyl complexes over that of the unsubstituted Cp complex is provided. In the catalytic systems with the former, it is possible to regenerate the active solvento complexes via protonation of the metal hydride intermediates and subsequent ligand substitution; this process is, however, very nonfacile in the catalytic system with the latter.
authors.affiliation: Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong, People's Republic of China.
authors.forename: Hung Wai
authors.initials: HW
authors.lastname: Cheung
authors.forename: Juan
authors.initials: J
authors.lastname: Li
authors.forename: Wenxu
authors.initials: W
authors.lastname: Zheng
authors.forename: Zhongyuan
authors.initials: Z
authors.lastname: Zhou
authors.forename: Yu Hin
authors.initials: YH
authors.lastname: Chiu
authors.forename: Zhenyang
authors.initials: Z
authors.lastname: Lin
authors.forename: Chak Po
authors.initials: CP
authors.lastname: Lau
mesh_terms: D000097:Acetonitriles / Q000138:chemical synthesis / Q000737:chemistry*; D000438:Alcohols / Q000138:chemical synthesis / Q000737:chemistry*; D000478:Alkylation; D006841:Hydrocarbons, Aromatic / Q000138:chemical synthesis / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D017975:Ruthenium Compounds / Q000737:chemistry*
chemical_list: D000097:Acetonitriles; D000438:Alcohols; D006841:Hydrocarbons, Aromatic; D017975:Ruthenium Compounds