A mechanistic study of the reaction between a diiron(II) complex [FeII(2)(mu-OH)2(6-Me3-TPA)2](2+) and O2 to form a diiron(III) peroxo complex

Inorganic Chemistry
S V KryatovLawrence Que

Abstract

A kinetic study of the reaction between a diiron(II) complex [Fe(II)(2)(mu-OH)(2)(6-Me(3)-TPA)(2)](2+) 1, where 6-Me(3)-TPA = tris(6-methyl-2-pyridylmethyl)amine, and dioxygen is presented. A diiron(III) peroxo complex [Fe(III)(2)(mu-O)(mu-O(2))(6-Me(3)-TPA)(2)](2+) 2 forms quantitatively in dichloromethane at temperatures from -80 to -40 degrees C. The reaction is first order in [Fe(II)(2)] and [O(2)], with the activation parameters DeltaH(double dagger) = 17 +/- 2 kJ mol(-1) and DeltaS(double dagger) = -175 +/- 20 J mol(-1) K(-1). The reaction rate is not significantly influenced by the addition of H(2)O or D(2)O. The reaction proceeds faster in more polar solvents (acetone and acetonitrile), but the yield of 2 is not quantitative in these solvents. Complex 1 reacts with NO at a rate about 10(3) faster than with O(2). The mechanistic analysis suggests an associative rate-limiting step for the oxygenation of 1, similar to that for stearoyl-ACP Delta(9)-desaturase, but distinct from the probable dissociative pathway of methane monoxygenase. An eta(1)-superoxo Fe(II)Fe(III) species is a likely steady-state intermediate during the oxygenation of complex 1.

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Citations

Jul 2, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Pascal SpechtSiegfried Schindler
Oct 16, 2004·Dalton Transactions : an International Journal of Inorganic Chemistry·Svetlana V PavlovaSunney I Chan
Sep 18, 2020·Chemical Communications : Chem Comm·Sylvain EngilbergeSeigo Shima
Apr 2, 2005·Proceedings of the National Academy of Sciences of the United States of America·Xiaopeng Shan, Lawrence Que
Jan 23, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Xianru SunElena V Rybak-Akimova
Jun 9, 2005·Chemical Reviews·Sergey V KryatovSiegfried Schindler
May 25, 2007·Accounts of Chemical Research·Ivan V KorendovychElena V Rybak-Akimova
Oct 26, 2002·Biochimica Et Biophysica Acta·H Yamini ShrivastavaBalachandran Unni Nair
Nov 11, 2003·Inorganic Chemistry·Miquel CostasLawrence Que
Jun 26, 2003·Journal of the American Chemical Society·Mark P MehnLawrence Que
Feb 12, 2004·Chemical Reviews·Edit Y Tshuva, Stephen J Lippard
Dec 23, 2004·Journal of the American Chemical Society·Nermeen W AboelellaWilliam B Tolman

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