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1,1′-bis(diphenylphosphino)ferrocene as an intramolecular or intermolecular bridging ligand related to the phenyl-functionalized diiron propanedithiolate complex: synthesis and catalysis of the reduction of protons


Reaction of the diiron propanedithiolate complex [μ-(SCH2)2CHC6H5]Fe2(CO)6 (A) with 1,1′-bis(diphenylphosphino)ferrocene (dppf) in refluxing xylene yielded an intramolecular bridged complex [(μ-SCH2)2CHC6H5]Fe2(CO)4(μ-dppf) (1), while in MeCN in the presence of Me3NO·2H2O gave an intermolecular bridged complex [(μ-SCH2)2CHC6H5Fe2(CO)5]2(μ,κ11-dppf) (2). The structures of both complexes were fully characterized by spectroscopic methods and X-ray crystallography. In the solid state, the diphosphine spans the iron–iron vector, adopting cis basal–basal arrangement as expected in intramolecular bridged complex 1, while the diphosphine connects the two [2Fe2S] clusters by coordinating one of the two Fe atoms of each [2Fe2S] cluster in intermolecular bridged complex 2. The Fe–Fe bond length of 2.63 Å in 1 is longer than that in 2, among the longest of Fe–Fe bonds in the synthetic active sites of Fe–Fe hydrogenases. Electrochemical investigation showed that complex 1 catalyzed the reduction of protons to give dihydrogen in the presence of HBF4, but did not catalyze the oxidation of dihydrogen in the presence of pyridine.

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This work is supported by the Chinese National Natural Science Foundation under Grant [No. 21072046]; the Chinese National Training Programs of Innovation and Entrepreneurship for Undergraduates under Grant (No. 201210467022).

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Correspondence to Chang-Gong Li.

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Li, C., Xue, F., Cui, M. et al. 1,1′-bis(diphenylphosphino)ferrocene as an intramolecular or intermolecular bridging ligand related to the phenyl-functionalized diiron propanedithiolate complex: synthesis and catalysis of the reduction of protons. Transition Met Chem 40, 47–52 (2015).

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  • MeCN
  • Ferrocene
  • Dihydrogen
  • Dppe
  • Diiron