Sonja's and Souvik's paper in Chem Comm


The work investigates how MOF confinement affects ligand substitution at the [Fe2(dcbdt)(CO)6] complex, which is a proton reduction catalyst.

Pullen, S., Roy, S. & Ott, S. [FeFe] Hydrogenase active site model chemistry in a UiO-66 metal–organic framework. Chem. Commun. (2017). doi: 10.1039/C7CC01620D


The reactivity of [Fe2(dcbdt)(CO)6] 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.

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