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

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.

SUBMITTER: Pullen S

PROVIDER: S-EPMC6095454 | biostudies-literature | 2017 May

REPOSITORIES: biostudies-literature

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

Pullen Sonja S Roy Souvik S Ott Sascha S

Chemical communications (Cambridge, England) 20170501 37

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] ...[more]

PMID: 28443863

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