Activation of C-H / H-H bonds by rhodium(II) porphyrin bimetalloradicals

Journal of the American Chemical Society
Weihong Cui, Bradford B Wayland

Abstract

Reactivity, kinetic, and thermodynamic studies are reported for reactions of a rhodium(II) bimetalloradical with H(2), and with the methyl C-H bonds for a series of substrates CH(3)R (R = H, CH(3), OH, C(6)H(5)) using a m-xylyl diether tethered diporphyrin ligand. Bimolecular substrate reactions involving the intramolecular use of two metalloradical centers and preorganization of the four-centered transition state (M*...X...Y*...M) result in large rate enhancements as compared to termolecular reactions of monometalloradicals. Activation parameters and deuterium kinetic isotope effects for the substrate reactions are reported. The C-H bond reactions become less thermodynamically favorable as the substrate steric requirements increase, and the activation free energy (DeltaG++) decreases regularly as DeltaG degrees becomes more favorable. An absolute Rh-H bond dissociation enthalpy of 61.1 +/- 0.4 kcal mol(-1) is directly determined, and the derived Rh-CH(2)R BDE values increase regularly with the increase in the C-H BDE.

References

Feb 20, 2002·Chemical Reviews·Alexander E. Shilov, Georgiy B. Shul'pin
May 31, 2002·Nature·Jay A Labinger, John E Bercaw
Feb 19, 2003·Accounts of Chemical Research·William D Jones
Apr 16, 2003·Accounts of Chemical Research·Stephen J Blanksby, G Barney Ellison
Apr 24, 2003·Journal of the American Chemical Society·Weihong CuiBradford B Wayland

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Citations

May 7, 2011·Chemical Reviews·Mar Gómez-Gallego, Miguel A Sierra
Oct 4, 2007·Chemical Communications : Chem Comm·Shan LiBradford B Wayland
Jul 10, 2009·Chemical Communications : Chem Comm·Jason B Love
May 8, 2010·Chemical Communications : Chem Comm·Jeroen WassenaarJarl Ivar van der Vlugt
May 21, 2015·Journal of the American Society for Mass Spectrometry·Guohua WuAnthony J Stace
Sep 1, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Wu YangKin Shing Chan
Jan 25, 2007·Chemistry : a European Journal·Gonzalo GivajaJason B Love
Jun 10, 2011·Angewandte Chemie·Helmut Schwarz
Dec 1, 2017·Chemical Society Reviews·Samuel J ThompsonGuangbin Dong
Apr 5, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Chun Ran LiuKin Shing Chan
Dec 17, 2009·Journal of the American Chemical Society·Florian F PuschmannBas de Bruin
Mar 5, 2010·Journal of the American Chemical Society·Noah L WiederDonald H Berry
Jun 29, 2021·Journal of the American Chemical Society·Yu ZhangThomas B Rauchfuss
Jun 30, 2012·Journal of the American Chemical Society·Ching Tat ToKin Shing Chan
Feb 7, 2014·Journal of the American Chemical Society·Anna Lewandowska-AndralojcEtsuko Fujita
Aug 29, 2013·Journal of the American Chemical Society·Marco G CrestaniDaniel J Mindiola
Apr 15, 2020·Journal of the American Chemical Society·Charles H Arnett, Theodor Agapie
Mar 29, 2014·Journal of the American Chemical Society·Yue Hu, Jack R Norton
Nov 15, 2011·Organic Letters·Lin ZhangQun Liu
Sep 28, 2018·Journal of the American Chemical Society·Máté J Bezdek, Paul J Chirik
Aug 14, 2020·Journal of the American Chemical Society·Ryan Patrick Coll, Kim R Dunbar
Aug 5, 2021·Chemistry : a European Journal·Phan T TruongMiriam A Bowring
Aug 10, 2007·Journal of the American Chemical Society·Claudia M FafardOleg V Ozerov

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