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[FeFe] Hydrogenase active site model chemistry in a UiO-66 metal–organic framework

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Abstract

The reactivity of [Fe2(dcbdt)(CO)6] (1) confined in a UiO-66(Zr) metal–organic framework towards CO ligand substitutions with phosphines of different sizes was investigated. The reaction with smaller phosphines (PX3, X = Me, Et) is more selective compared to analogous reactions in homogenous solution phase, and two CO ligands at up to 80% of all [FeFe] sites in UiO-66–1 are replaced. The produced [Fe2(dcbdt)(CO)4(PX3)2] complexes in the UiO-66 matrix behave like typical [FeFe] hydrogenase active site model complexes, are reduced at more cathodic potentials than their hexacarbonyl analogues, and form bridging hydrides under acidic conditions.

Graphical abstract: [FeFe] Hydrogenase active site model chemistry in a UiO-66 metal–organic framework

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Publication details

The article was received on 02 Mar 2017, accepted on 19 Apr 2017 and first published on 19 Apr 2017


Article type: Communication
DOI: 10.1039/C7CC01620D
Citation: Chem. Commun., 2017, Advance Article
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    [FeFe] Hydrogenase active site model chemistry in a UiO-66 metal–organic framework

    S. Pullen, S. Roy and S. Ott, Chem. Commun., 2017, Advance Article , DOI: 10.1039/C7CC01620D

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