Autocatalytic oxidative addition of PhBr to Pd(PtBu3)2 via Pd(PtBu3)2(H)(Br).

Journal of the American Chemical Society
Fabiola Barrios-LanderosJohn F Hartwig

Abstract

We report that oxidative addition of bromobenzene to Pd(PtBu3)2 occurs by an unusual autocatalytic mechanism. Studies on the effect of various additives showed that the degree of rate acceleration followed the trend: (PtBu3)Pd(Ph)(Br) approximately (HPtBu3)Br < [(PtBu3)Pd(mu-Br)]2 < (PtBu3)2Pd(H)(Br). Studies on the reactions of Pd(PtBu3)2 in the presence of (PtBu3)2Pd(H)(Br) showed that the concentration of (PtBu3)2Pd(H)(Br) decreased only after the Pd(0) complex had been consumed. These data indicated that the catalyst in this process is (PtBu3)2Pd(H)(Br). Thermal decomposition of the three-coordinate oxidative addition product (PtBu3)Pd(Ar)(Br) during the reaction of Pd(PtBu3)2 and bromoarenes ultimately leads to formation of (PtBu3)2Pd(H)(Br). Parallel reactions of bromobenzene with (PtBu3)2Pd(H)(Br) and Pd(PtBu3)2 showed that the bromoarenes reacted considerably faster with the Pd(II) species than with the Pd(0) species. We therefore propose a catalytic cycle for oxidative addition in which PBut3.HBr reacts with the Pd(0) species to form (PtBu3)2Pd(H)(Br), and (PtBu3)2Pd(H)(Br) reacts with the bromoarene, possibly though the anionic species [HPtBu3+][(PtBu3)Pd(Br)-], to form [Pd(PtBu3)(Ar)(Br)].

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Citations

Sep 1, 2012·Chemical Reviews·Percia Beatrice ArockiamPierre H Dixneuf
May 25, 2011·Journal of the American Chemical Society·Emmanuel Ferrer FlegeauAnny Jutand
Jul 24, 2012·Journal of the American Chemical Society·Dominik M OhlmannLukas J Goossen
Dec 5, 2008·Journal of the American Chemical Society·Kanwal J SinghDavid B Collum
Dec 18, 2009·Journal of the American Chemical Society·Brad P Carrow, John F Hartwig
Sep 6, 2011·The Journal of Organic Chemistry·Alexander C Hoepker, David B Collum
Oct 12, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Christos E KefalidisEric Clot
Oct 22, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Claire L McMullinNatalie Fey
May 7, 2015·Journal of the American Chemical Society·Steven A TymonkoScott E Denmark
May 7, 2015·Journal of the American Chemical Society·Steven A TymonkoScott E Denmark
May 11, 2012·Angewandte Chemie·Carin C C Johansson SeechurnVictor Snieckus
Jun 19, 2013·Chemistry : a European Journal·Sabrina BaaderLukas J Gooßen
Oct 16, 2013·Angewandte Chemie·Andrew J Bissette, Stephen P Fletcher
May 20, 2015·Chemistry : a European Journal·Jeffrey S QuesnelBruce A Arndtsen
Apr 4, 2017·The Journal of Organic Chemistry·Russell F AlgeraDavid B Collum
Aug 6, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Claire L McMullinJeremy N Harvey
Jul 8, 2018·Nature Communications·Silvia CorezziCristiano De Michele
Sep 20, 2017·Organic & Biomolecular Chemistry·Waqar Rauf, John M Brown
Oct 16, 2020·Angewandte Chemie·Christoph FrickeFranziska Schoenebeck
Oct 30, 2008·Journal of the American Chemical Society·Alexey G SergeevMatthias Beller
Dec 25, 2008·Inorganic Chemistry·Shanshan ChenXingwei Li
Aug 29, 2019·ACS Omega·Tsukasa SawatoMasahiko Yamaguchi

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