Oxidative addition of biphenylene and chlorobenzene to a Rh(CNC) complex

The synthesis and organometallic chemistry of rhodium(I) complex Rh(CNC-Me)(SOMe 2 )BAr F 4 , featuring NHC-based pincer and labile dimethyl sulfoxide ligands, is reported. This complex reacts with biphenylene and chlorobenzene to afford products resulting from selective C–C and C–Cl bond activation, Rh(CNC-Me)(2,2’-biphenyl)(OSMe 2 )BAr F 4 and Rh(CNC-Me)(Ph)Cl(OSMe 2 )BAr F 4 , respectively. A detailed DFT-based computational analysis indicates that C–H bond oxidative addition of these substrates is kinetically competitive, but in all cases endergonic: contrasting the large thermodynamic driving force calculated for insertion of the metal into the C–C and C–Cl bonds, respectively. Under equivalent conditions the substrates are not activated by the phosphine-based pincer complex Rh(PNP- i Pr)(SOMe 2 )BAr F 4