Redox behaviour of ([fc(NPiPr2)2]Fe)2, formation of an iron–iron bond and cleavage of azobenzene

Fraser S. Pick; Daniel B. Leznoff; Michael D. Fryzuk

doi:10.1039/C8DT00828K

Redox behaviour of ([fc(NPⁱPr₂)₂]Fe)₂, formation of an iron–iron bond and cleavage of azobenzene†‡

Fraser S. Pick,^a Daniel B. Leznoff

*^b and Michael D. Fryzuk

*^a

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^a Department of Chemistry, The University of British Columbia, 2036 Main Mall, Vancouver, BC, Canada
E-mail: fryzuk@chem.ubc.ca
Fax: +1 604-822-2847
Tel: +1 604 -822-2897

^b Deprtment of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby, BC, Canada V5A 1S6
E-mail: dleznoff@sfu.ca
Fax: +1 778-782-3765
Tel: +1 778 -782-4887

Abstract

The redox behaviour of the dimeric tetrairon complex, ([fc(NPⁱPr₂)₂]Fe)₂ (where fc(NPⁱPr₂)₂ = 1,1′-(C₅H₄NPⁱPr₂)₂Fe) has been investigated. Upon reduction with KC₈ an Fe–Fe bond is formed with the complex maintaining a high spin configuration and having the formula [K(THF)₆]([fc(NPⁱPr₂)₂]Fe)₂. In contrast, oxidation of the complex is ligand based; for example, addition of the 1,2-diiodoethane (I₂ equivalent) results in the formation of the monomeric iron(II) diiodide [fc(NⁱPr₂I)₂]FeI₂ wherein the phosphine is oxidized. The dimeric tetrairon complex reacts photolytically with azobenzene, cleaving the N [double bond, length as m-dash] N double bond and forming the new monomeric bis(phosphoramidate) iron complex. [fc(NP(NPh)ⁱPr₂)₂]Fe. Characterization of these paramagnetic complexes was accomplished by magnetic susceptibility studies and X-ray analyses.

This article is part of the themed collection: In celebration of Richard Andersen’s 75th birthday

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DOI: https://doi.org/10.1039/C8DT00828K
Article type: Paper
Submitted: 03 ⵎⴰⵕ 2018
Accepted: 26 ⵢⵓⵏ 2018
First published: 26 ⵢⵓⵏ 2018

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Dalton Trans., 2018,47, 10925-10931

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Redox behaviour of ([fc(NPⁱPr₂)₂]Fe)₂, formation of an iron–iron bond and cleavage of azobenzene

F. S. Pick, D. B. Leznoff and M. D. Fryzuk, Dalton Trans., 2018, 47, 10925 DOI: 10.1039/C8DT00828K

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