Synthesis, structures and electrochemical properties of nitro- and amino-functionalized diiron azadithiolates as active site models of Fe-only hydrogenases |
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Authors: | Liu Tianbiao Wang Mei Shi Zhan Cui Hongguang Dong Weibing Chen Jiesheng Akermark Björn Sun Licheng |
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Institution: | State Key Laboratory of Fine Chemicals, Dalian University of Technology, Zhongshan Road 158-46, Dalian 116012, China. |
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Abstract: | Complex (mu-SCH2)2N(4-NO2C6H4)]Fe2(CO)6] (4) was prepared by the reaction of the dianionic intermediate (mu-S)2Fe2(CO)6](2-) and N,N-bis(chloromethyl)-4-nitroaniline as a biomimetic model of the active site of Fe-only hydrogenase. The reduction of 4 by Pd-C/H2 under a neutral condition afforded complex (mu-SCH2)2N(4-NH2C6H4)]Fe2(CO)6] (5) in 67 % yield. Both complexes were characterized by IR, 1H and 13C NMR spectroscopy and MS spectrometry. The molecular structure of 4, as determined by X-ray analysis, has a butterfly 2Fe2S core and the aryl group on the bridged-N atom slants to the Fe(2) site. Cyclic voltammograms of 4 and 5 were studied to evaluate their redox properties. It was found that complex 4 catalyzed electrochemical proton reduction in the presence of acetic acid. A plausible mechanism of the electrocatalytic proton reduction is discussed. |
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Keywords: | bioinorganic chemistry cluster compounds diiron azadithiolate iron‐only hydrogenase redox chemistry |
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