Theoretical approaches to estimating homolytic bond dissociation energies of organocopper and organosilver compounds

Abstract

Although organocopper and organosilver compounds are known to decompose by homolytic pathways among others, surprisingly little is known about their bond dissociation energies (BDEs). In order to address this deficiency, the performance of the DFT functionals BLYP, B3LYP, BP86, TPSSTPSS, BHandHLYP, M06L, M06, M06-2X, B97D, and PBEPBE, along with the double hybrids, mPW2-PLYP, B2-PLYP, and the ab initio methods, MP2 and CCSD(T), have been benchmarked against the thermochemistry for the M-C homolytic BDEs (D0) of Cu-CH3 and Ag-CH3, derived from guided ion beam experiments and CBS limit calculations (D0(Cu-CH3) = 223 kJ̇mol-1; D0(Ag-CH3) = 169 kJ̇mol -1). Of the tested methods, in terms of chem..