Thioether-ligated iron(II) and iron(III)-hydroperoxo/alkylperoxo complexes with an H-bond donor in the second coordination sphere

Leland R. Widger; Yunbo Jiang; Alison C. McQuilken; Tzuhsiung Yang; Maxime A. Siegler; Hirotoshi Matsumura; Pierre Moënne-Loccoz; Devesh Kumar; Sam P. de Visser; David P. Goldberg

doi:10.1039/C4DT00281D

Thioether-ligated iron(ii) and iron(iii)-hydroperoxo/alkylperoxo complexes with an H-bond donor in the second coordination sphere†

Leland R. Widger,^a Yunbo Jiang,^a Alison C. McQuilken,^a Tzuhsiung Yang,^a Maxime A. Siegler,^a Hirotoshi Matsumura,^b Pierre Moënne-Loccoz,*^b Devesh Kumar,^cd Sam P. de Visser*^c and David P. Goldberg*^a

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* Corresponding authors

^a Department of Chemistry, The Johns Hopkins University, 3400 North Charles Street, Baltimore, Maryland 21218, USA
E-mail: dpg@jhu.edu
Fax: +1-410-516-8420
Tel: +1-410-516-6658

^b Oregon Health & Science University, Institute of Environmental Health, Mail code: HRC3, 3181 SW Sam Jackson Park Road, Portland, OR 97239, USA
E-mail: moennelo@ohsu.edu
Fax: +1-503-346-3427
Tel: +1-503-346-3429

^c Manchester Institute of Biotechnology and School of Chemical Engineering and Analytical Science, The University of Manchester, 131 Princess Street, Manchester, UK
E-mail: sam.devisser@manchester.ac.uk

^d Department of Applied Physics, School of Physical Sciences, Babasaheb, Bhimrao Ambedkar University, Vidya Vihar, Rae Bareilly Road, Lucknow 226-025, India
E-mail: dkclcre@yahoo.com

Abstract

The non-heme iron complexes, [Fe^II(N3PySR)(CH₃CN)](BF₄)₂ (1) and [Fe^II(N3Py^amideSR)](BF₄)₂ (2), afford rare examples of metastable Fe(III)-OOH and Fe(III)-OOtBu complexes containing equatorial thioether ligands and a single H-bond donor in the second coordination sphere. These peroxo complexes were characterized by a range of spectroscopic methods and density functional theory studies. The influence of a thioether ligand and of one H-bond donor on the stability and spectroscopic properties of these complexes was investigated.

Dalton Transactions

Thioether-ligated iron(ii) and iron(iii)-hydroperoxo/alkylperoxo complexes with an H-bond donor in the second coordination sphere†

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Thioether-ligated iron(II) and iron(III)-hydroperoxo/alkylperoxo complexes with an H-bond donor in the second coordination sphere

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