Mechanism of catalytic hydration of nitriles with hydrotris(pyrazolyl)borato (Tp) ruthenium complexes
作者： Chung Wing Leung , Wenxu Zheng , Zhongyuan Zhou , Zhenyang Lin , Chak Po Lau
DOI: 10.1021/OM800474W
关键词:
摘要: The aquo-amido complexes TpRu(PPh3)(H2O)(NHC(O)R) (R = Me, Ph), which can be prepared by refluxing a THF solution of TpRu(PPh3)(RCN)H containing excess water or more conveniently reacting TpRu(PPh3)(RCN)Cl with NaOH in the presence water, are found to active for catalytic hydration nitriles amides. catalysis proceeds via mechanism that is distinctly different from common ones involving intramolecular nucleophilic attack hydroxo (or aquo) ligand external hydroxide ion water) at carbon atom η1-coordinated nitrile form metal amide intermediate and subsequent protonation amido an adjacent aquo solvent water. new involves intermediacy relatively stable complex chelating N-imidoylimidato ligand; ring-opening this product-generating step. Formation several steps. The...
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