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2020-05-25Zeitschriftenartikel DOI: 10.1002/ijch.202000038
Redox Potentials of High‐Valent Iron‐, Cobalt‐, and Nickel‐Oxido Complexes: Evidence for Exchange Enhanced Reactivity
dc.contributor.authorComba, Peter
dc.contributor.authorLöhr, Anna‐Maria
dc.contributor.authorPfaff, Florian
dc.contributor.authorRay, Kallol
dc.date.accessioned2021-06-17T20:04:26Z
dc.date.available2021-06-17T20:04:26Z
dc.date.issued2020-05-25none
dc.date.updated2020-12-07T10:50:24Z
dc.identifier.urihttp://edoc.hu-berlin.de/18452/23661
dc.description.abstractThe ferrocene titration method has been employed to determine the one‐electron reduction potentials of a series of oxido‐iron(IV), oxido‐cobalt(IV) and oxido/hydroxido‐nickel(III) complexes based on the same tetradentate TMG3tren ligand (TMG3tren=tris[2‐(N‐tetramethylguanidyl)ethyl]amine). The S=2 ground state of the [(TMG3tren)FeIV=O]2+ complex allows an exchange enhanced reactivity, which enables it to perform efficient oxygen atom transfer (OAT) and hydrogen atom abstraction (HAA) reactions with a low one‐electron reduction potential of 270 mV vs. SCE. In the absence of exchange enhanced reactivity, the OAT and HAA abilities of the S=3/2 [(TMG3tren)CoIV−O(Sc(OTf)3)]2+, S=1/2 [(TMG3tren)NiIII−O(H)]2+ and the previously reported S=1 [(TMC)(CH3CN)FeIV=O]2+ and [(N4Py)FeIV=O]2+ complexes can be directly correlated to their reduction potentials. Notably, [(N4Py)FeIV=O]2+ and [(TMG3tren)FeIV=O]2+ exhibit similar OAT and HAA reactivities although the reduction potential of [(N4Py)FeIV=O]2+ is 0.24 V more positive than that of [(TMG3tren)FeIV=O]2+. The present study therefore provides experimental evidence for exchange enhanced reactivity and rationalizes nature's choice for employing S=2 oxido‐iron(IV) cores to achieve difficult oxidation reactions at biologically viable potentials.eng
dc.description.sponsorshipHeidelberg University
dc.description.sponsorshipDeutsche Forschungsgemeinschaft http://dx.doi.org/10.13039/501100001659
dc.language.isoengnone
dc.publisherHumboldt-Universität zu Berlin
dc.rights(CC BY 4.0) Attribution 4.0 Internationalger
dc.rights.urihttps://creativecommons.org/licenses/by/4.0/
dc.subjectexchange enhanced reactivityeng
dc.subjecthigh-valent metal-oxido complexeseng
dc.subjectreduction potentialeng
dc.subjectnon heme ironeng
dc.subjectlate transition metalseng
dc.subject.ddc540 Chemie und zugeordnete Wissenschaftennone
dc.titleRedox Potentials of High‐Valent Iron‐, Cobalt‐, and Nickel‐Oxido Complexes: Evidence for Exchange Enhanced Reactivitynone
dc.typearticle
dc.identifier.urnurn:nbn:de:kobv:11-110-18452/23661-1
dc.identifier.doi10.1002/ijch.202000038none
dc.identifier.doihttp://dx.doi.org/10.18452/22994
dc.type.versionpublishedVersionnone
local.edoc.container-titleIsrael Journal of Chemistrynone
local.edoc.pages6none
local.edoc.type-nameZeitschriftenartikel
local.edoc.institutionMathematisch-Naturwissenschaftliche Fakultätnone
local.edoc.container-typeperiodical
local.edoc.container-type-nameZeitschrift
local.edoc.container-publisher-placeWeinheimnone
dc.description.versionPeer Reviewednone
local.edoc.container-articlenumber60none
dc.identifier.eissn1869-5868
local.edoc.affiliationComba, Peter; Universität Heidelberg Anorganisch-Chemisches Institut, INF 270 D-69120 Heidelberg Germanynone
local.edoc.affiliationLöhr, Anna‐Maria; Universität Heidelberg Anorganisch-Chemisches Institut, INF 270 D-69120 Heidelberg Germanynone
local.edoc.affiliationPfaff, Florian; Department of Chemistry Humboldt-Universität zu Berlin Brook-Taylor-Strasse 2 Berlin Germany 12489none
local.edoc.affiliationRay, Kallol; Department of Chemistry Humboldt-Universität zu Berlin Brook-Taylor-Strasse 2 Berlin Germany 12489none

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