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          Institute: MPI für bioanorganische Chemie     Collection: MPI für bioanorganische Chemie     Display Documents

ID: 708690.0, MPI für bioanorganische Chemie / MPI für bioanorganische Chemie
Dramatic Influence of an Anionic Donor on the Oxygen-Atom Transfer Reactivity of a MnV Oxo Complex.
Authors:Neu, Heather M.; Quesne, Matthew G.; Yang, Tzuhsiung; Prokop-Prigge, Katharine A.; Lancaster, Kyle M.; Donohoe, James; DeBeer, Serena; de Visser, Sam P.; Goldberg, David P.
Date of Publication (YYYY-MM-DD):2014
Title of Journal:Chemistry-A European Journal
Journal Abbrev.:Chem.Eur.J.
Issue / Number:45
Start Page:14584
End Page:14588
Review Status:Peer-review
Audience:Experts Only
Abstract / Description:Addition of an anionic donor to an Mn-V(O) porphyrinoid complex causes a dramatic increase in 2-electron oxygen-atom-transfer (OAT) chemistry. The 6-coordinate [Mn-V(O)(TBP(8)Cz)(CN)](-) was generated from addition of Bu4N+CN- to the 5-coordinate Mn-V(O) precursor. The cyanide-ligated complex was characterized for the first time by Mn K-edge X-ray absorption spectroscopy (XAS) and gives MnO=1.53 angstrom, MnCN=2.21 angstrom. In combination with computational studies these distances were shown to correlate with a singlet ground state. Reaction of the CN- complex with thioethers results in OAT to give the corresponding sulfoxide and a 2e(-)-reduced Mn-III(CN)(-) complex. Kinetic measurements reveal a dramatic rate enhancement for OAT of approximately 24000-fold versus the same reaction for the parent 5-coordinate complex. An Eyring analysis gives H=14kcalmol(-1), S=-10calmol(-1)K(-1). Computational studies fully support the structures, spin states, and relative reactivity of the 5- and 6-coordinate Mn-V(O) complexes.
External Publication Status:published
Document Type:Article
Communicated by:N. N.
Affiliations:MPI für bioanorganische Chemie
External Affiliations:[Neu,H.P.;Yang,T.;Prokop-Prigge,K.A.; Goldberg,D.P.;] Johns Hopkins Univ., Dept.Chem., Baltimore, MD 21218 USA.
[ Quesne,M.G.; de Visser,S.P.;] Univ.Manchester, Manchester Inst.Biotechnol., Manchester, Lancs, England.
[Lancaster,K.M.; Donohoe,J.;] Cornell Univ, Dept Chem & Chem Biol, Ithaca, NY 14850 USA.
Identifiers:ISI:000344358900006 [ID No:1]
ISSN:0947-6539 [ID No:2]
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