Phosphine-containing Diiron Propane-1,2-dithiolate Derivatives: Synthesis, Spectroscopy, X-ray Crystal Structures, and E
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Phosphine‑containing Diiron Propane‑1,2‑dithiolate Derivatives: Synthesis, Spectroscopy, X‑ray Crystal Structures, and Electrochemistry Lin Yan1 · Jun Yang2 · Shuang Lü3 · Xu‑Feng Liu1 · Yu‑Long Li2 · Xing‑Hai Liu4 · Zhong‑Qing Jiang5 Received: 24 July 2020 / Accepted: 30 October 2020 © Springer Science+Business Media, LLC, part of Springer Nature 2020
Abstract Biomimics for the active site of [FeFe]-hydrogenases, have been synthesized and characterized. Treatment of [ Fe 2 (CO) 6 {μ-SCH 2 CH(CH 3 )S}] (1) and phosphine ligands tris(2-furyl)phosphine, tri(m-tolyl)phosphine, bis(diphenylphosphino)methane (dppm), or 1,2-bis(diphenylphosphino)benzene (dppbz) with Me3NO·2H2O as the decarbonylation agent afforded the corresponding phosphine-containing derivatives [Fe2(CO)5(L){μ-SCH2CH(CH3)S}] (L = P(2C4H3O)3, 2; P(3-C6H4CH3)3, 3; Ph2PCH2PPh2, 4) and [Fe2(CO)4{κ2-(Ph2P)2(1,2-C6H4)}{μ-SCH2CH(CH3)S}] (5) in moderate to good yields. The new complexes 2‒5 have been structurally characterized by elemental analysis, IR, NMR spectroscopy, and further confirmed by X-ray diffraction analysis. The electrochemistry of complexes 2‒5 have been investigated by cyclic voltammetry, showing that they can catalyze the reduction of protons to H2 in the presence of HOAc. Graphic abstract
1/2H2
1/2H2
OC OC
S Fe
OC
S Fe
L
OC
e e
OC OC
CO CO
S Fe
S Fe
Ph2 P P Ph2 CO
H+
H+
Keywords [FeFe]-hydrogenases · Diiron propane-1,2-dithiolate · Phosphine ligand · X-ray crystal structure · Electrochemistry
Electronic supplementary material The online version of this article (https://doi.org/10.1007/s10562-020-03450-2) contains supplementary material, which is available to authorized users. * Xu‑Feng Liu [email protected] 1
School of Materials and Chemical Engineering, Ningbo University of Technology, Ningbo 315211, China
College of Chemistry and Environmental Engineering, Sichuan University of Science and Engineering, Zigong 643000, China
2
3
School of Pharmacy, Liaocheng University, Liaocheng 252059, China
4
College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China
5
Department of Physics, Key Laboratory of ATMMT Ministry of Education, Zhejiang Sci-Tech University, Hangzhou 310018, China
13
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L. Yan et al.
1 Introduction
2 Experimental
Great efforts have been devoted to the development of new efficient and earth abundant metal containing catalysts for the production of H2 to find out a potential pathway for solving the energy crisis [1‒3]. [FeFe]-hydrogenases are of great interest owing to their high efficiency in producing H2 in some microorganisms [4‒6]. Since the elucidation of the crystal structure of [FeFe]-hydrogenases, numerous efforts have been paid to the biomimetic chemistry of the active site of [FeFe]-hydrogenases [7‒10]. Previous studies have reported the crystal structure of the active site of [FeFe]-hydrogenases, which is featuring a binuclear Fe core, a bridging three-atom azadithiolate, cyanides, carbonyls, and a [Fe4S4]-cont
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