Synthetic and structural study on some new porphyrin or metalloporphyrin macrocycle-containing model complexes for the active site of [FeFe]-hydrogenases

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• 作者：Li-Cheng Song ; Liang-Xing Wang ; Chang-Gong Li ; Fengyu Li ; Zhongfang Chen
• 关键词：Enzyme model ; Hydrogenase ; Iron ; Metalloporphyrin ; Porphyrin ; Sulfur
• 刊名：Journal of Organometallic Chemistry
• 出版年：1 January, 2014
• 年：2014
• 卷：749
• 期：Complete
• 页码：120-128
• 全文大小：1271 K

文摘

To mimick the natural enzymes [FeFe]-hydrogenases, some new porphyrin and metalloporphyrin moiety-containing model complexes, namely 5-[p-Fe₂(CO)₆(渭-SCH₂)₂CHO₂CC₆H₄],10,15,20-triphenylporphyrin聽(2), 5-[p-Fe₂(CO)₆(渭-SCH₂)₂CHO₂CC₆H₄],10,15,20-triphenylporphyrinozinc (3), 5-[p-Fe₂(CO)₆(渭-SCH₂)₂NC₂H₄SC₆H₄],10,15,20-triphenylporphyrin (7), and 5-[p-Fe₂(CO)₅(渭-SCH₂)₂NC₂H₄SC₆H],10,15,20-triphenylporphyrin (8), have been successfully prepared by our designed synthetic routes involving the corresponding precursor compounds [(渭-SCH₂)₂CHO₂CC₆H₄CHO-p]Fe₂(CO)₆ (1), p-Boc-NHC₂H₄SC₆H₄CHO (4), 5-(p-Boc-NHC₂H₄SC₆H₄),10,15,20-triphenylporphyrin (5), and 5-(p-NH₂C₂H₄ SC₆H₄),10,15,20-triphenylporphyrin (6). All these new compounds 1-8 have been characterized by elemental analysis and various spectroscopic methods, and particularly for 1-3 and 7 by X-ray crystallography. In addition, the density functional theory computations on 8 were performed to assist its structural characterization.