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Spectroscopic and theoretical investigation of the [Fe 2 (bdt)(CO) 6 ] hydrogenase mimic and some catalyst intermediates

DOI: 10.1039/C9CP01393H DOI Help

Authors: Jean-pierre Oudsen (University of Amsterdam) , Bas Venderbosch (University of Amsterdam) , David Martin (University of Amsterdam) , Ties Johannis Korstanje (University of Amsterdam) , Joost N. H. Reek (University of Amsterdam) , Moniek Tromp (University of Amsterdam)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Physical Chemistry Chemical Physics

State: Published (Approved)
Published: May 2019
Diamond Proposal Number(s): 13069

Abstract: In [Fe-Fe] hydrogenase mimic systems the ene-1,2-dithiolene ligands play an important role in the stabilisation of the redox- active metal center. This is demonstrated by the benzenedithiolene (bdt) analogue, featuring six terminal carbonyl ligands connected to a di-iron metal center, i.e. [Fe2(bdt)(CO)6]. Here we present a combined experimental and theoretical study that elucidates key intermediates [Fe2(bdt)(CO)6]1- and [Fe2(bdt)(µ-CO)(CO)5]2- in the electrocatalytic production of dihydrogen. A DFT study shows that [Fe2(bdt)(CO)6]1- is the kinetic product after the first one electron reduction, while the previously proposed bridging intermediate species [Fe2(bdt)(µ-CO)(CO)5]1- is kinetically inaccessible. The doubly reduced species [Fe2(bdt)(µ-CO)(CO)5]2- was for the first time structurally characterized using EXAFS. XANES analysis confirms the existence of reduced iron zero species and confirms the distorted geometry that was suggested by the DFT calculations. Combining IR, UV-Vis and XAS spectroscopic results with TD-DFT and FEFF calculations enabled us to assign the key-intermediate [Fe2(bdt)(CO)6]2-. This study emphasizes the strengths of combining computational chemistry with advanced spectroscopy techniques.

Subject Areas: Chemistry

Instruments: B18-Core EXAFS