Altered mechanisms of reactions of phosphate esters bridging a dinuclear metal center

Journal of the American Chemical Society
Tim HumphryAlvan C Hengge

Abstract

Kinetic isotope effects in the nucleophile and leaving group were obtained for the reaction of p-nitrophenyl phosphate monoester coordinated to a dinuclear Co(III) complex. The metal complex of the p-nitrophenyl phosphate monoester was found to hydrolyze by a single-step concerted mechanism, with significant nucleophilic participation in the transition state. By contrast, the hydrolysis of uncomplexed p-nitrophenyl phosphate occurs by a very loose transition state with little bond formation to the nucleophile. Previously, the metal complex of the diester methyl-p-nitrophenyl phosphate was found to hydrolyze via a two-step addition-elimination mechanism, in contrast to the concerted hydrolysis mechanism followed by uncomplexed diesters with the p-nitrophenolate leaving group. These results show that coordination to a metal complex can significantly alter the mechanism of phosphoryl transfer.

References

Aug 1, 1990·FASEB Journal : Official Publication of the Federation of American Societies for Experimental Biology·W W Cleland
Nov 1, 1995·Chemistry & Biology·S J Admiraal, D Herschlag
Feb 20, 2002·Accounts of Chemical Research·Alvan C Hengge
Sep 13, 2002·Journal of the American Chemical Society·Adam G CassanoMichael E Harris
Dec 12, 2002·Journal of the American Chemical Society·Tim HumphryAlvan C Hengge

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Citations

Jan 16, 2013·Quarterly Reviews of Biophysics·Shina C L KamerlinArieh Warshel
Jul 31, 2010·Journal of the American Chemical Society·Michael E HarrisVernon E Anderson
Aug 14, 2009·Journal of the American Chemical Society·Guoqiang FengNicholas H Williams
Sep 10, 2009·Journal of the American Chemical Society·David R EdwardsR Stan Brown
Nov 26, 2008·Dalton Transactions : an International Journal of Inorganic Chemistry·Olga TaranAnatoly K Yatsimirsky
Jun 4, 2013·Physical Chemistry Chemical Physics : PCCP·Fernanda DuarteShina Caroline Lynn Kamerlin
Jul 24, 2013·Proceedings of the National Academy of Sciences of the United States of America·Hong GuMichael E Harris
Apr 26, 2011·Annual Review of Biochemistry·Jonathan K LassilaDaniel Herschlag
Dec 31, 2004·Proceedings of the National Academy of Sciences of the United States of America·Gerhard SchenkLuke W Guddat
Oct 28, 2008·Current Opinion in Chemical Biology·Michael E Harris, Adam G Cassano
May 6, 2015·Biochimica Et Biophysica Acta·Michael E HarrisDarrin M York
Jun 22, 2007·Organic & Biomolecular Chemistry·Shina C L Kamerlin, John Wilkie
Jan 18, 2006·Chemistry : a European Journal·Federico PepiMarco Di Stefano
Jun 10, 2011·Organic & Biomolecular Chemistry·Shina C L Kamerlin, John Wilkie
May 1, 2012·Chemical Communications : Chem Comm·Fabrizio MancinPaolo Tecilla
Mar 21, 2009·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Shina C L KamerlinArieh Warshel
Aug 10, 2006·Chemical Reviews·W Wallace Cleland, Alvan C Hengge
Dec 21, 2006·Journal of the American Chemical Society·Jill RawlingsAlvan C Hengge
Aug 5, 2009·Methods : a Companion to Methods in Enzymology·John K Frederiksen, Joseph A Piccirilli

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