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Synthesis, characterization and DFT studies of 1, 1′-Bis(diphenylphosphino)ferrocene substituted diiron complexes: Bioinspired [FeFe] hydrogenase model complexes

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Abstract

The reaction of [Fe2(CO)6(μ-toluene-3, 4-benzenedithiolate)] 1 and bidentate diphosphine, 1, 1′-bis(diphenylphosphino)ferrocene (dppf) has been studied. New complexes obtained have been characterized by various spectroscopic techniques as bioinspired models of the iron hydrogenase active site. The crystal structure of [Fe2(CO)5(κ 1-dppfO)(μ-toluene-3, 4-benzenedithiolate)] 4 is reported.

New iron carbonyl complexes were synthesized from the reaction of [Fe2(CO)6(μ-toluene-3, 4-benzenedithiolate)] 1 and bidentate diphosphine, 1, 1’-bis(diphenylphosphino)ferrocene (dppf). Complex 2 was catalytically active towards proton reduction in presence of acetic acid. Based on DFT calculations the HOMO and LUMO in complex 2 were found to be localized on the Fe centers of the two {Fe2S2} units.

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Acknowledgements

The author thanks Department of Science & Technology (DST), India for financial support (SR/S1/IC-28/2011). Dr. S. M. Mobin is gratefully acknowledged for crystallographic measurements of complex 4. SKG is thankful to University of Delhi for providing R & D grant. RBS and AS are grateful to IIT Bombay computer centre for computational resources.

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Authors and Affiliations

  1. Department of Chemistry, University of Delhi, Delhi, 110007, India

    SANDEEP KAUR-GHUMAAN

  2. Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, 400076, India

    A SREENITHYA & RAGHAVAN B SUNOJ

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  1. SANDEEP KAUR-GHUMAAN
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Correspondence to SANDEEP KAUR-GHUMAAN.

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Supplementary Information

Supplementary data related to this article can be found on the journal website: www.ias.ac.in/chemsci. CCDC 887865 contains the crystallographic data for 4. Copies of this information can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (Fax: + 44-1223-336033; e-mail: deposit@ccdc.cam.uk or www.ccdc.cam.ac.uk).

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KAUR-GHUMAAN, S., SREENITHYA, A. & SUNOJ, R.B. Synthesis, characterization and DFT studies of 1, 1′-Bis(diphenylphosphino)ferrocene substituted diiron complexes: Bioinspired [FeFe] hydrogenase model complexes. J Chem Sci 127, 557–563 (2015). https://doi.org/10.1007/s12039-015-0809-y

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