Affiliation:
1. State Key Laboratory of Chemical Resource Engineering Beijing University of Chemical Technology 100029 Beijing P. R. China
Abstract
AbstractThe electronic effects of the bidentate ligands play a vital role in the transition metal‐catalyzed conjugate addition reactions. Here, the insertion step (rate‐determining step (RDS) of the conjugate addition) catalyzed by Pd(II)/Rh(I)‐complexes with 26 bipyridine‐type (bpy) ligands linking different substituent groups in the opposite sides (C4, C4′ position) are systematically studied by density functional theory (DFT). It is found that for both Pd(II)‐ and Rh(I)‐catalysis, the stronger the electron‐withdrawing group connecting to both C4 and C4′ positions of bpy ligands can promote the insertion step. The predominance of π‐back donation in Rh(I) and σ‐donation in Pd(II) is the main reason for above different electronic properties of Pd(II) and Rh(I)‐catalysis. This work gives enough theoretical guide to the rational design of the efficient transition metal‐based catalyst for conjugate addition.
Funder
National Natural Science Foundation of China
Fundamental Research Funds for the Central Universities
Subject
Organic Chemistry,Physical and Theoretical Chemistry