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A Bispidine Iron(IV)-Oxo Complex in the Entatic State

Title
A Bispidine Iron(IV)-Oxo Complex in the Entatic State
Authors
Comba, PeterFukuzumi, ShunichiKoke, CarstenMartin, BodoLoehr, Anna-MariaStraub, Johannes
Ewha Authors
Shunichi Fukuzumi
SCOPUS Author ID
Shunichi Fukuzumiscopus
Issue Date
2016
Journal Title
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
ISSN
1433-7851JCR Link1521-3773JCR Link
Citation
vol. 55, no. 37, pp. 11129 - 11133
Keywords
coordination chemistrydensity functional calculationshomogeneous catalysisiron bispidine complexesredox potentials
Publisher
WILEY-V C H VERLAG GMBH
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
For a series of Fe-IV=O complexes with tetra- and pentadentate bispidine ligands, the correlation of their redox potentials with reactivity, involving a variety of substrates for alkane hydroxylation (HAT), alkene epoxidation, and phosphine and thioether oxidation (OAT) are reported. The redox potentials span approximately 350mV and the reaction rates over 8 orders of magnitude. From the experimental data and in comparison with published studies it emerges that electron transfer and the driving force are of major importance, and this is also supported by the DFT-based computational analysis. The striking difference of reactivity of two isomeric systems with pentadentate bispidines is found to be due to a destabilization of the S=1 ground state of one of the ferryl isomers, and this is supported by the experimentally determined redox potentials and published stability constants with a series of first-row transition metal ions with these two isomeric ligands.
DOI
10.1002/anie.201605099
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자연과학대학 > 화학·나노과학전공 > Journal papers
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