title: Rational design of model Pd(ii)-catalysts for C-H activation involving ligands with charge-shift bonding characteristics.
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)PdBr2complex (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 sp2carbons. Our density functional theory calculation results suggest that the (bis-2BB)PdBr2catalysts outperform the popular (bis-NHC)PdBr2complex 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.
authors.affiliation: Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi'an, 710062, China. zcjwh@snnu.edu.cn.
authors.forename: Dongxia
authors.initials: D
authors.lastname: Ma
authors.affiliation: Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi'an, 710062, China. zcjwh@snnu.edu.cn.
authors.forename: Congjie
authors.initials: C
authors.lastname: Zhang
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, MOE Laboratory for Computational Physical Science, Department of Chemistry, Fudan University, Shanghai, 200433, China. xxchem@fudan.edu.cn.
authors.forename: Zhe-Ning
authors.initials: ZN
authors.lastname: Chen
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, MOE Laboratory for Computational Physical Science, Department of Chemistry, Fudan University, Shanghai, 200433, China. xxchem@fudan.edu.cn.
authors.forename: Xin
authors.initials: X
authors.lastname: Xu