Synthesis, characterization, and H/D exchange of μ-hydride-containing [FeFe]-hydrogenase subsite models formed by protonation reactions of (μ-TDT)Fe2(CO)4(PMe3)2 (TDT = SCH2SCH2S) with protic acids

Li-Cheng Song; An-Guo Zhu; Yuan-Qiang Guo

doi:10.1039/c5dt04297f

Synthesis, characterization, and H/D exchange of μ-hydride-containing [FeFe]-hydrogenase subsite models formed by protonation reactions of (μ-TDT)Fe2(CO)4(PMe3)2 (TDT = SCH2SCH2S) with protic acids

Dalton Trans. 2016 Mar 28;45(12):5021-9. doi: 10.1039/c5dt04297f.

Authors

Li-Cheng Song¹, An-Guo Zhu¹, Yuan-Qiang Guo¹

Affiliation

¹ Department of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China. [email protected] and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin 300071, China.

PMID: 26777138
DOI: 10.1039/c5dt04297f

Abstract

As [FeFe]-hydrogenase models, the first thiodithiolate (TDT) ligand-containing μ-hydride complexes [(μ-TDT)Fe2(CO)4(PMe3)2(μ-H)](+)Y(-) (2-7, Y = Cl, ClO4, PF6, BF4, CF3CO2, CF3SO3) have been prepared by protonation reactions of (μ-TDT)Fe2(CO)4(PMe3)2 (1) with the corresponding HY acids. While the protonation reactions are monitored by in situ(1)H and (31)P{(1)H} NMR spectroscopy to show the isomer type and stability of 2-7, the structures of the isolated 2-7 are characterized by elemental analysis, spectroscopy and for some of them by X-ray crystallography. Although the H/D exchange of μ-hydride complex 7 (Y = CF3SO3) with D2 or D2O has been proved not to occur under the studied conditions, the H/D exchange of 7 with DCl gives the μ-deuterium complex [(μ-TDT)Fe2(CO)4(PMe3)2(μ-D)](+)[CF3SO3](-) (8) in a nearly quantitative yield. To our knowledge, 8 is the first crystallographically characterized μ-deuterium-containing butterfly [2Fe2S] complex produced by H/D exchange reaction.

Publication types

Research Support, Non-U.S. Gov't