Dithiolato- and Diselenolato-Bridged Nickel–Iron Biomimetics for the Active Site of [NiFe]Hydrogenases
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- 作者：Li-Cheng SongYu Lu ; Liang Zhu ; Qian-Li Li
- 刊名：Organometallics
- 出版年：2017
- 出版时间：February 13, 2017
- 年：2017
- 卷：36
- 期：3
- 页码：750-760
- 全文大小：556K
- ISSN：1520-6041
文摘
As the active site models of [NiFe]hydrogenases, three types of dichalcogenido E (E = S, Se)-bridged NiFe complexes (dppb)Ni[μ-E(CH2)3E-μ]Fe(CO)3 (dppb = bis(1,2-diphenylphosphino)benzene, 2a, E = S; 2b, E = Se), {(dppb)Ni[μ-E(CH2)3E-μ](μ-H)Fe(CO)3}BF4 (3a, E = S; 3b, E = Se), and {(dppb)Ni[μ-E(CH2)3E-μ](μ-D)Fe(CO)3}BF4 (4a, E = S; 4b, E = Se) were prepared by starting from the precursors (dppb)Ni[μ-E(CH2)3E-μ] (1a, E = S; 1b, E = Se) in satisfactory yields. While coordinations of 1a,b with Fe2(CO)9 gave the first-type dichalcogenido-bridged models 2a,b, the protonations of 2a,b with HBF4·Et2O afforded the second-type dichalcogenido-bridged μ-hydride models 3a,b the oxidative additions of 2a,b with DCl followed by anionic exchanges of the resulting intermediates with NaBF4 produced the third-type dichalcogenido-bridged μ-deuteride models 4a,b. Models 2a,b–4a,b were all fully characterized by elemental analysis, spectroscopy, and X-ray crystallography, and the H/D exchange reactions of μ-hydrides 3a,b with D2 and D2O were further studied under light irradiation by 1H and 2H NMR spectroscopy.