Reinvestigation of the formation of a mononuclear Fe(III) hydroperoxido complex using high pressure kinetics

Dalton Transactions : an International Journal of Inorganic Chemistry
Thomas NebeSiegfried Schindler

Abstract

Previous stopped flow kinetic experiments suggested an interchange associative mechanism for the ligand substitution reaction, [Fe(bztpen)(OMe)](2+) + H(2)O(2)--> {[Fe(bztpen)(OMe)(HOOH)](2+)}(++)--> [Fe(bztpen)(OOH)](2+) + MeOH (bztpen = N-benzyl-N, N',N'tris(2-methylpyridyl)-ethylenediamine). Thus a seven-coordinate transition state containing both the leaving methoxide and the incoming hydrogen peroxide ligands was proposed. On the basis of high pressure kinetic data we can now conclude that this is not the case since the rate of the reaction is independent of pressure for the formation of the purple low spin transient hydroperoxido complex, [Fe(bztpen)(OOH)](2+). [Fe(bztpen)(OOH)](2+) has so far proved to be too short-lived for solid state isolation. As part of our ongoing pursuit of this elusive species we have structurally characterised the nitrosyl and acetate iron(II) complexes, [Fe(bztpen)(NO)](OTf)(2) and [Fe(bztpen)(OAc)](BPh(4)), as well as the air stable Co(II) complexes [Co(bztpen)Cl)]BF(4), [Co(metpen)Cl]SbF(6) and [Co(bztpen)(OAc)]BPh(4). We did not realise our aim of accessing stable Co(III) hydroperoxido or peroxido complexes by reaction of the cobalt complexes with H(2)O(2).

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Citations

Aug 26, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Mads S VadChristine J McKenzie
Mar 19, 2015·Inorganic Chemistry·Norma Ortega-VillarVíctor M Ugalde-Saldívar
Nov 28, 2016·Spectrochimica Acta. Part A, Molecular and Biomolecular Spectroscopy·Yang SongCynthia M Dupureur
Nov 1, 2017·Chemistry : a European Journal·Christina WegebergChristine J McKenzie
Jul 16, 2016·Chemistry : a European Journal·Lucía Piñeiro-LópezJosé A Real
Jul 2, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Pascal SpechtSiegfried Schindler
Dec 2, 2018·European Journal of Inorganic Chemistry·Atanu BanerjeeFerman A Chavez
Sep 10, 2013·Chemical Communications : Chem Comm·Peili ZhangLicheng Sun
Dec 10, 2016·Inorganic Chemistry·Bongki ShinJaeheung Cho

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