Peer-Reviewed Journal Details
Mandatory Fields
Kynman, AE;Lau, S;Dowd, SO;Kramer, T;Chaplin, AB
2020
October
European Journal of Inorganic Chemistry
Oxidative Addition of Biphenylene and Chlorobenzene to a Rh(CNC) Complex
Published
2 ()
Optional Fields
CARBON-CARBON BOND C-C BOND PALLADIUM(II) COMPLEXES POLARIZATION FUNCTIONS ARYL HALIDES BASIS-SETS H BONDS RHODIUM CATALYST ISOMERIZATION
The synthesis and organometallic chemistry of rhodium(I) complex [Rh(CNC-Me)(SOMe2)][BAr4F], 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)(OSMe2)][BAr4F] and [Rh(CNC-Me)(Ph)Cl(OSMe2)][BAr4F], 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-iPr)(SOMe2)][BAr4F].
WEINHEIM
1434-1948
10.1002/ejic.202000780
Grant Details