{1,1′‐(Dimethylsilylene)bis[methanechalcogenolato]}diiron Complexes [2Fe2E(Si)] (E=S, Se, Te) – [FeFe] Hydrogenase Models

(Bis‐selenolato) and (bis‐tellurolato)diiron complexes [2Fe2E(Si)] were prepared and compared with the known (bis‐thiolato)diiron complex A to assess their ability to produce hydrogen from protons. Treatment of [Fe 3 (CO) 12 ] with 4,4‐dimethyl‐1,2,4‐diselenasilolane ( 1 ) in boiling toluene afforded hexacarbonyl{ μ ‐{[1,1′‐(dimethylsilylene)bis[methaneselenolato‐ κSe  :  κSe ]](2 −)}}diiron( FeFe ) ( 2 ). The analog bis‐tellurolato complex hexacarbonyl{μ‐{[1,1′‐(dimethylsilylene)bis[methanetellurolato‐ κTe  :  κTe ]](2 −)}}diiron( FeFe ) ( 3 ) was obtained by treatment of [Fe 3 (CO) 12 ] with dimethylbis(tellurocyanatomethyl)dimethylsilane, which was prepared in situ. All compounds were characterized by NMR, IR spectroscopy, mass spectrometry, elemental analysis and single‐crystal X‐ray analysis. The electrocatalytic properties of the [2Fe2X(Si)] (X=S, Se, Te) model complexes A, 1 , and 2 towards hydrogen formation were evaluated.