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Nickel Fluorocarbene Metathesis with Fluoroalkenes
Author(s) -
Harrison Daniel J.,
Daniels Alex L.,
Guan Jia,
Gabidullin Bulat M.,
Hall Michael B.,
Baker R. Tom
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201802090
Subject(s) - metathesis , alkene , carbene , nickel , trifluoromethyl , chemistry , salt metathesis reaction , yield (engineering) , limiting , organic chemistry , medicinal chemistry , catalysis , materials science , polymerization , polymer , alkyl , metallurgy , mechanical engineering , engineering
Alkene metathesis with directly fluorinated alkenes is challenging, limiting its application in the burgeoning field of fluoro‐organic chemistry. A new nickel tris(phosphite) fluoro(trifluoromethyl)carbene complex ([P 3 Ni]=CFCF 3 ) reacts with CF 2 =CF 2 (TFE) or CF 2 =CH 2 (VDF) to yield both metallacyclobutane and perfluorocarbene metathesis products, [P 3 Ni]=CF 2 and CR 2 =CFCF 3 (R=F, H). The reaction of [P 3 Ni]=CFCF 3 with trifluoroethylene also yields metathesis products, [P 3 Ni]=CF 2 and cis / trans ‐CFCF 3 =CFH. However, unlike reactions with TFE and VDF, this reaction forms metallacyclopropanes and fluoronickel alkenyl species, resulting presumably from instability of the expected metallacyclobutanes. DFT calculations and experimental evidence established that the observed metallacyclobutanes are not intermediates in the formation of the observed metathesis products, thus highlighting a novel variant of the Chauvin mechanism enabled by the disparate four‐coordinate transition states.