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Issue 21, 2013
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Mechanistic studies on proton transfer in a [FeFe] hydrogenase mimic complex

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Abstract

Four different pathways for deprotonation of [(μ-pdt){Fe(CO)3}{Fe(CO)(κ2-Me2PCH2N(Me)CH2PMe2)}] (pdt = propane-1,3-dithiolate) [1Hμ]1+ were examined, including (1) the “Direct” deprotonation; (2) the “Indirect” deprotonation via the pendant amine N; (3) the “Indirect” deprotonation via the distal metal Fe; and (4) the “Indirect” deprotonation via the dithiolate S. Only deprotonation of the “Indirect” pathway via the pendant amine N is feasible at room temperature. The most favorable migration destination for the bridging hydride in [1Hμ]1+ is the pendant amine N (activation energy barrier 16.1 kcal mol−1). Migrations to the other two possible sites including the distal metal Fe (34.6 kcal mol−1) and the S in the dithiolate group (41.5 kcal mol−1) were hindered by high proton shuttling barriers. Once the migration barriers of those three “Indirect” pathways are overcome, the following deprotonations from all three positions including the distal atom Fe, the dithiolate S and the pendant amine N, are all feasible. The results also demonstrate a large difference for deprotonation of the hydride from the terminal and bridging sites. The low energy of the virtual orbital associated with the antibonding M–H interaction of [1HFe]1+ implies the high activity for the interaction with aniline.

Graphical abstract: Mechanistic studies on proton transfer in a [FeFe] hydrogenase mimic complex

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Publication details

The article was received on 25 Dec 2012, accepted on 20 Mar 2013 and first published on 21 Mar 2013


Article type: Paper
DOI: 10.1039/C3DT33087G
Citation: Dalton Trans., 2013,42, 7816-7822
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    Mechanistic studies on proton transfer in a [FeFe] hydrogenase mimic complex

    Y. Wang and M. S. G. Ahlquist, Dalton Trans., 2013, 42, 7816
    DOI: 10.1039/C3DT33087G

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