Revealing the mechanism of Rh(I)-catalyzed hydroformylation of 4-pyridylethene derivatives: DFT study

摘要

A comprehensive theoretical investigation into the mechanism of 1-phenyl-1-(4-pyridyl)ethene hydroformylation, using a rhodium catalyst employing a nonlocal density functional method (B3LYP), was carried out. The calculated results show that it is strongly exothermic by > 90 kj/mol of the whole catalytic cycle, and the rate-limited step is H-2 oxidative addition. The regioselectivity originates from olefin insertion into the Rh-H bond. The predominant product is the regiospecifically 3-phenyl-3-(4-pyridal)propanal determined both thermodynamically and kinetically. These are in agreement with practicality experimental studies. (c) 2006 Wiley Periodicals, Inc.