Rational design of model Pd(ii)-catalysts for C–H activation involving ligands with charge-shift bonding characteristics. Issue 3 (6th January 2017) - Ma, Dongxia
Abstract : A palladium(ii ) complex with a bis-2-borabicyclo[1.1.0]but-1(3)-ene ligand having charge-shift bonding characteristics contributes to better performance for C–H bond activation. Abstract : In this work, five new palladium(ii ) complexes have been designed as the model catalysts for methane to methyl trifluoroacetate conversion. All these compounds are analogues of the well-established (bis-NHC)PdBr2 complex (NHC, N-heterocyclic carbenes), derived by complexing the palladium(ii ) metal ion with the derivatives of bis-2-borabicyclo[1.1.0]but-1(3)-ene (bis-2BB) ligands using the sp 2 carbons. Our density functional theory calculation results suggest that the (bis-2BB)PdBr2 catalysts outperform the popular (bis-NHC)PdBr2 complex in the desired catalytic process, and further reveal that the charge-shift bonding in the bis-2BB ligands contributes to the improved catalytic performance. These findings may spark new ideas for experimental design of more efficient organometallic catalysts for C–H bond activation and functionalization.