Dialkylamino cyclopentadienyl ruthenium(ii) complex-catalyzed α-alkylation of arylacetonitriles with primary alcohols

Autor: Wenxu Zheng, Hung Wai Cheung, Zhenyang Lin, Chak Po Lau, Juan Li, Yu Hin Chiu, Zhongyuan Zhou
Rok vydání: 2010
Předmět:
Zdroj: Dalton Trans.. 39:265-274
ISSN: 1477-9234
1477-9226
DOI: 10.1039/b917805h
Popis: 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.
Databáze: OpenAIRE