Models of the iron-only hydrogenase: Reactions of [Fe2(CO)6(μ-pdt)] with small bite-angle diphosphines yielding bridge and chelate diphosphine complexes [Fe2(CO)4(diphosphine)(μ-pdt)]

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)

“…Complexes 1-4 were prepared according to published methods [24,26,27,57] (see ESI for details). IR spectra were recorded on a Nicolet 6700 FT-IR spectrometer in a solution cell fitted with calcium fluoride plates, subtraction Electronic supplementary material The online version of this article…”

“…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].…”

“…Herein we detail a comparative investigation of the electrochemistry and proton-reduction behaviour of diiron and diruthenium complexes [M 2 (CO) 4 (ldppm)(l-pdt)] [24,27,57] and [M 2 (CO) 4 (l-dppm)(l-edt)] [26,27,57] (Fig. 1). …”

“…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].…”

Binuclear Copper(I) Borohydride Complex Containing Bridging Bis(diphenylphosphino) Methane Ligands: Polymorphic Structures of [(µ2-dppm)2Cu2(η2-BH4)2] Dichloromethane Solvate

“…Such compounds are of great interest due to their catalytic activity including the transformation of small molecules on metal centres [8,9], they can also be used as synthetic models of enzyme action [10][11][12].…”