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Issue 30, 2017
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Dithiolato- and halogenido-bridged nickel–iron complexes related to the active site of [NiFe]-H2ases: preparation, structures, and electrocatalytic H2 production

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Abstract

A new series of the structural and functional models for the active site of [NiFe]-H2ases has been prepared by a simple and convenient synthetic route. Thus, treatment of diphosphines RN(PPh2)2 (1a, R = p-MeC6H4CH2; 1b, R = EtO2CCH2) with an equimolar NiCl2·6H2O, NiBr2·3H2O, and NiI2 in refluxing CH2Cl2/MeOH or EtOH gave the mononuclear Ni complexes RN(PPh2)2NiX2 (2a, R = p-MeC6H4CH2, X = Cl; 2b, R = EtO2CCH2, X = Cl; 3a, R = p-MeC6H4CH2, X = Br; 3b, R = EtO2CCH2, X = Br; 4a, R = p-MeC6H4CH2, X = I; 4b, R = EtO2CCH2, X = I) in 67–97% yields. Further treatment of complexes 2a,b–4a,b with an equimolar mononuclear Fe complex (dppv)(CO)2Fe(pdt) and NaBF4 resulted in formation of the targeted model complexes [RN(PPh2)2Ni(μ-pdt)(μ-X)Fe(CO)(dppv)](BF4) (5a, R = p-MeC6H4CH2, X = Cl; 5b, R = EtO2CCH2, X = Cl; 6a, R = p-MeC6H4CH2, X = Br; 6b, R = EtO2CCH2, X = Br; 7a, R = p-MeC6H4CH2, X = I; 7b, R = EtO2CCH2, X = I) in 60–96% yields. All the new complexes 3a,b–4a,b and 5a,b–7a,b have been characterized by elemental analysis and spectroscopy, and particularly for some of them (3a,b/4a,b and 5b/6b) by X-ray crystallography. More interestingly, the electrochemical and electrocatalytic properties of such halogenido-bridged model complexes are first studied systematically and particularly they have been found to be pre-catalysts for proton reduction to H2 under CV conditions.

Graphical abstract: Dithiolato- and halogenido-bridged nickel–iron complexes related to the active site of [NiFe]-H2ases: preparation, structures, and electrocatalytic H2 production

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Publication details

The article was received on 17 Jun 2017, accepted on 13 Jul 2017 and first published on 14 Jul 2017


Article type: Paper
DOI: 10.1039/C7DT02203D
Citation: Dalton Trans., 2017,46, 10003-10013
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    Dithiolato- and halogenido-bridged nickel–iron complexes related to the active site of [NiFe]-H2ases: preparation, structures, and electrocatalytic H2 production

    L. Song, X. Han, W. Chen, J. Li and X. Wang, Dalton Trans., 2017, 46, 10003
    DOI: 10.1039/C7DT02203D

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