950579-45-0Relevant academic research and scientific papers
A new route to the synthesis of phosphine-substituted diiron azaand oxadithiolate complexes
He, Jiao,Deng, Cheng-Long,Li, Yao,Li, Yu-Long,Wu, Yu,Zou, Li-Ke,Mu, Chao,Luo, Qiang,Xie, Bin,Wei, Jian,Hu, Jing-Wen,Zhao, Pei-Hua,Zheng, Wen
, p. 1322 - 1330 (2017)
Diiron dithiolate complexes have received special attention because of their structural similarity to the active site of [FeFe]-hydrogenases, which are the most efficient and fastest catalysts for the generation of dihydrogen in nature. Recently, we established a novel and efficient way to prepare phosphine-substituted diiron aza- and oxadithiolate complexes. Reaction of Fe2(μ-SCH2OH)2(CO)6 and several phosphine ligands L (L = PPh3, PPh2(2-C5H4N), P(C6H4-4-CH3)3) affords the intermediate Fe2(μ-SCH2OH)2(CO)5L, while the intermediate in situ reacts with primary amines RNH2 (R = CH2CH2CH(CH3)2, CH2CH2CH2SCH3, C6H4-4-CH3) to produce the target phosphine- substituted diiron azadithiolate complexes Fe2[(μ- SCH2)2NCH2CH2CH(CH3)2](CO)5(PPh3) (1), Fe2[(μ-SCH2)2NCH2CH2CH(CH3)2](CO)5[PPh2(2-C5H4N)] (2), Fe2[(μ- SCH2)2NCH2CH2CH(CH3)2](CO)5[P(C6H4-4-CH3)3] (3), Fe2[(μ-SCH2)2NCH2CH2CH2SCH3](CO)5(PPh3) (4), Fe2[(μ- SCH2)2NCH2CH2CH2SCH3](CO)5[PPh2(2-C5H4N)] (5), Fe2[(μ-SCH2)2NCH2CH2CH2SCH3](CO)5[P(C6H4-4-CH3)3] (6), Fe2[(μ-SCH2)2N C6H4-4-CH3](CO)5[PPh2(2-C5H4N)] (7), and Fe2[(μ-SCH2)2N C6H4-4-CH3](CO)5[P(C6H4-4-CH3)3] (8) in moderate yields. A novel complex Fe2[(μ-SCH2)2NCH2CH2PPh2](CO)5 (9) can be obtained by reaction of Fe2(μ- SCH2OH)2(CO)6 and Ph2PCH2CH2NH2. In addition, according to the same strategy, phosphine-substituted diiron oxadithiolate complexes Fe2[(μ-SCH2)2O](CO)5[P(C6H4-4-F)3] (10), Fe2[(μ-SCH2)2O](CO)5[P(C6H4-4-CH3)3] (11), and Fe2[(μ-SCH2)2O](CO)5(Ph2PCH2CH3) (12) have been successfully synthesized. All of the new complexes 1-12 were fully characterized by elemental analysis, IR, and NMR spectroscopy, and particularly for 1-4, 6, 7, and 9-11 by X-ray single diffraction analysis. Moreover, complexes 1 and 10 were found to be catalysts for H2 production under electrochemical conditions.
