The "innocent" role of Sc3+ on a non-heme Fe catalyst in an O2 environment

Albert Poater, Sai V. C. Vummaleti, Luigi Cavallo

Research output: Contribution to journalArticlepeer-review

4 Scopus citations


Density functional theory calculations have been used to investigate the reaction mechanism proposed for the formation of an oxoiron(iv) complex [Fe IV(TMC)O]2+ (P) (TMC = 1,4,8,11-tetramethylcyclam) starting from a non-heme reactant complex [FeII(TMC)]2+ (R) and O2 in the presence of acid H+ and reductant BPh4 -. We also addressed the possible role of redox-inactive Sc3+ as a replacement for H+ acid in this reaction to trigger the formation of P. Our computational results substantially confirm the proposed mechanism and, more importantly, support that Sc 3+ could trigger the O2 activation, mainly dictated by the availability of two electrons from BPh4 -, by forming a thermodynamically stable Sc3+-peroxo-Fe3+ core that facilitates O-O bond cleavage to generate P by reducing the energy barrier. These insights may pave the way to improve the catalytic reactivity of metal-oxo complexes in O2 activation at non-heme centers. This journal is © the Partner Organisations 2014.
Original languageEnglish (US)
Pages (from-to)11190
JournalDalton Transactions
Issue number29
StatePublished - 2014

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: A.P. thanks the Spanish MIClNN for a Ramon y Cajal contract (RYC-2009-05226) and the European Commission for a Career Integration Grant (CIG09-GA-2011-293900). We thank Prof. Lawrence Que Jr for helpful comments.

ASJC Scopus subject areas

  • Inorganic Chemistry


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