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Oxidative Addition of Biphenylene and Chlorobenzene to a Rh(CNC) Complex
Author(s) -
Kynman Amy E.,
Lau Samantha,
Dowd Sean O.,
Krämer Tobias,
Chaplin Adrian B.
Publication year - 2020
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202000780
Subject(s) - chemistry , biphenylene , chlorobenzene , oxidative phosphorylation , oxidative addition , organic chemistry , catalysis , biochemistry , polymer , phenylene
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 ].