Hydrogenase biomimetics with redox-active ligands: Electrocatalytic proton reduction by [Fe2(CO)4(κ2-diamine)(μ-edt)] (diamine = 2,2′-bipy, 1,10-phen)

Abstract

Hydrogenase biomimetics with redox-active ligands: Electrocatalytic proton reduction by [Fe2(CO)4(2-diamine)(edt)] (diamine = 2,2-bipy, 1,10-phen). POLYHEDRON.

Hydrogenase biomimetics: structural and spectroscopic studies on diphosphine-substituted derivatives of Fe2(CO)6(µ-edt) (edt = ethanedithiolate) and Fe2(CO)6(µ-tdt) (tdt = 1,3-toluenedithiolate)

“…In comparison to the volume of work on pdt-bridged diiron hydrogenase biomimics, relatively little attention has been paid to related models containing an edt-bridge [18][19][20][21].…”

“…Recently, we have synthesized two edt-bridged diiron complexes Fe 2 (CO) 4 (κ 2 -diamine)(μedt) containing diamine ligands, and investigated their electrocatalytic properties [21].…”

Electrocatalytic properties of diiron ethanedithiolate complexes containing benzoate ester

“…The structural information promoted chemists to synthesize a variety of diiron hexacarbonyl complexes with the aim of mimicking the active site. In addition, some ligands such as phosphines, carbenes, thioethers and pyridine have been introduced to the diiron center by carbonyl substitution of the all‐carbonyl complexes. In the work reported in this paper, we utilized some phosphine ligands as surrogates for the cyanide found in the natural enzymes because: (i) such phosphine ligands are stable and easily available; (ii) in contrast to cyanide‐containing diiron complexes, the phosphine‐containing complexes are stable in the solid state and in solution; and (iii) the phosphine‐substituted complexes are more easily protonated, similar to cyanide …”

A comparative study of the electrochemical and proton-reduction behaviour of diphosphine-dithiolate complexes [M2(CO)4(μ-dppm){μ-S(CH2) n S}] (M = Fe, Ru; n = 2, 3)

“…Diphosphines have been widely used in this context and can either bridge the diiron centre or chelate to one end, bridging complexes, [Fe 2 (CO) 4 -(l-diphosphine)(l-dithiolate)] being thermodynamically stable with respect to isomeric chelate complexes [Fe 2 (CO) 4 -(j 2 -diphosphine)(l-dithiolate)]. Consequently a large number of diphosphine-bridged diiron-dithiolate complexes have been reported [23][24][25][26][27][28][29][30][31][32] but surprisingly little attention has been paid to their proton-reduction chemistry [27][28][29][30][31][32] even though some, for example [Fe 2 (CO) 4 (l-dppf)(l-pdt)] (dppf = 1,1 0 -bis(diphenylphosphino)ferrocene), have been shown to be efficient proton-reduction catalysts [29]. Similarly, given the large number of diiron complexes tested as proton-reduction catalysts, related diruthenium complexes have not been widely studied [53][54][55][56].…”

“…Consequently a large number of diphosphine-bridged diiron-dithiolate complexes have been reported [23][24][25][26][27][28][29][30][31][32] but surprisingly little attention has been paid to their proton-reduction chemistry [27-32] even though some, for example [Fe 2 (CO) 4 (l-dppf)(l-pdt)] (dppf = 1,1 0 -bis(diphenylphosphino)ferrocene), have been shown to be efficient proton-reduction catalysts [29]. Similarly, given the large number of diiron complexes tested as proton-reduction catalysts, related diruthenium complexes have not been widely studied [53][54][55][56].…”