Jump to main content
Jump to site search

Issue 44, 2016
Previous Article Next Article

Effect of the S-to-S bridge on the redox properties and H2 activation performance of diiron complexes related to the [FeFe]-hydrogenase active site

Author affiliations

Abstract

Three biomimetic models of the [FeFe]-hydrogenase active site, namely diiron dithiolates of [(μ-edt){Fe(CO)3}{Fe(CO)(κ2-PNP)}] (1, edt = ethane-1,2-dithiolate, PNP = Ph2PCH2N(nPr)CH2PPh2), [(μ-bdtMe){Fe(CO)3}{Fe(CO)(κ2-PNP)}] (2, bdtMe = 4-methylbenzene-1,2-dithiolate), and [(μ-adtBn){Fe(CO)3}{Fe(CO)(κ2-PNP)}] (3, adtBn = N-benzyl-2-azapropane-1,3-dithiolate), were prepared and structurally characterized. These complexes feature the same PNP ligand but different S-to-S bridges. Influence of the S-to-S bridge on the electrochemical properties and chemical oxidation reactivity of 1–3 was studied by cyclic voltammetry and by in situ IR spectroscopy. The results reveal that the S-to-S bridge has a considerable effect on the oxidation reactivity of 1–3 and on the stability of in situ generated single-electron oxidized complexes, [1]+, [2]+, and [3]+. The performances of [1]+ and [2]+ for H2 activation were explored in the presence of a mild chemical oxidant, while rapid decomposition of [3]+ thwarted the further study of this complex. Gratifyingly, 1 was found to be catalytically active, although in a low turnover number, for H2 oxidation in the presence of excess mild oxidant and a proton trapper under 1 atm H2 at room temperature.

Graphical abstract: Effect of the S-to-S bridge on the redox properties and H2 activation performance of diiron complexes related to the [FeFe]-hydrogenase active site

Back to tab navigation

Supplementary files

Publication details

The article was received on 26 Jul 2016, accepted on 04 Oct 2016 and first published on 04 Oct 2016


Article type: Paper
DOI: 10.1039/C6DT02953A
Citation: Dalton Trans., 2016,45, 17687-17696
  •   Request permissions

    Effect of the S-to-S bridge on the redox properties and H2 activation performance of diiron complexes related to the [FeFe]-hydrogenase active site

    M. Cheng, M. Wang, D. Zheng and L. Sun, Dalton Trans., 2016, 45, 17687
    DOI: 10.1039/C6DT02953A

Search articles by author

Spotlight

Advertisements