Dialkylamino cyclopentadienyl ruthenium(ii) complex-catalyzed alpha-alkylation of arylacetonitriles with primary alcohols.
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.
Cheung
Hung Wai
HW
Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong, People's Republic of China.
Li
Juan
J
Zheng
Wenxu
W
Zhou
Zhongyuan
Z
Chiu
Yu Hin
YH
Lin
Zhenyang
Z
Lau
Chak Po
CP
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*
D000097:Acetonitriles; D000438:Alcohols; D006841:Hydrocarbons, Aromatic; D017975:Ruthenium Compounds