Mimicking the protein access channel to a metal center: effect of a funnel complex on dissociative versus associative copper redox chemistry

Journal of the American Chemical Society
Nicolas Le PoulYves Le Mest

Abstract

The control of metal-ligand exchange in a confined environment is of primary importance for understanding thermodynamics and kinetics of the electron transfer process governing the reactivity of enzymes. This study reveals an unprecedented change of the Cu(II)/Cu(I) binding and redox properties through a subtle control of the access to the labile site by a protein channel mimic. The cavity effect was estimated from cyclic voltammetry investigations by comparison of two complexes displaying the same coordination sphere (tmpa) and differing by the presence or absence of a calix[6]arene cone surrounding the metal labile site L. Effects on thermodynamics are illustrated by important shifts of E(1/2) toward higher values for the calix complexes. This is ascribable to the protection of the labile site of the open-shell system from the polar medium. Such a cavity control also generates specific stabilizations. This is exemplified by an impressively exalted affinity of the calixarene system for MeCN, and by the detection of a kinetic intermediate, a noncoordinated DMF guest molecule floating inside the cone. Kinetically, a unique dissymmetry between the Cu(I) and Cu(II) ligand exchange capacity is highlighted. At the CV time scale, the...Continue Reading

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Citations

Mar 10, 2010·Journal of the American Chemical Society·Benoit ColassonOlivia Reinaud
Nov 5, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Antoine GomilaYves Le Mest
Mar 13, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Ana Gabriela Porras GutiérrezNicolas Le Poul
Mar 15, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Yi-Hsueh HoJwu-Ting Chen
Mar 29, 2014·Langmuir : the ACS Journal of Surfaces and Colloids·Sébastien LhenryPhilippe Hapiot
Jul 23, 2014·Journal of the American Chemical Society·Yanchuan ZhaoTimothy M Swager
Jul 30, 2015·Organic & Biomolecular Chemistry·Md Monarul IslamTakehiko Yamato
Apr 5, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Mariane Le FurRaphaël Tripier
Oct 17, 2014·Chemical Society Reviews·Jean-Noël RebillyOlivia Reinaud
Oct 30, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Antoine GomilaYves Le Mest
Feb 11, 2011·Angewandte Chemie·Rafael Gramage-DoriaLoïc Toupet
Mar 11, 2016·European Journal of Organic Chemistry·Yanchuan Zhao, Timothy M Swager
Jun 24, 2015·Accounts of Chemical Research·Nicolas Le PoulOlivia Reinaud

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