Investigations on the Synthesis,Structural Characterization,and Crystal Structures of Three Diiron and Tetrairon Azadithiolate Complexes |
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| Authors: | Li‐Ke Zou Cheng‐Long Deng Yao Li Jiao He Jian Wei Yu Wu Bin Xie Pei‐Hua Zhao Yu‐Long Li |
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| Affiliation: | 1. College of Chemistry and Environmental Engineering, Sichuan University of Science & Engineering, Zigong, P. R. China;2. Institute of Functional Materials, Sichuan University of Science & Engineering, Zigong, P. R. China;3. School of Materials Science and Engineering, North University of China, Taiyuan, P. R. China |
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| Abstract: | Three diiron and tetrairon azadithiolate complexes as models for the active site of [FeFe] hydrogenase were prepared. Reaction of complex Fe2(SCH2OH)2(CO)6 and NH2CH2CH2CH2OCH3 resulted in the diiron azadithiolate hexcarbonyl complex Fe2[(SCH2)2NCH2CH2CH2OCH3](CO)6 ( 1 ) in moderate yield. Furthermore, treatment of complex 1 with mono phosphine ligand PPh3 and diphosphine ligand Ph2PCH2CH2PPh2 in the presence of decarbonylation reagent Me3NO · 2H2O yielded the phosphine‐substituted azadithiolate complexes Fe2[(SCH2)2NCH2CH2CH2OCH3]CO)5(PPh3) ( 2 ) and {Fe2[(SCH2)2NCH2CH2CH2OCH3](CO)5}2(Ph2PCH2CH2PPh2) ( 3 ) respectively. The new complexes 1 – 3 were fully characterized by elemental analysis, IR, 1H, 13C, 31P NMR spectroscopy and X‐ray crystallography. It is worthy to note that the crystallographic studies show the unusual difference of the methoxypropanyl substituent on the N atom of complexes 1 and 2 , largely because of the affection of phosphine ligand PPh3. In addition, complex 1 was found to be a catalyst for H2 production under electrochemical condition. |
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| Keywords: | Hydrogenase Synthesis Phosphine X‐ray crystallography Iron |
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