Synthesis, Structure, and Electrocatalysis of Butterfly [Fe2SP] Cluster Complexes Relevant to [FeFe]-Hydrogenases

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• 作者：Li-Cheng Song ; Zhen-Chao Gu ; Wei-Wei Zhang ; Qian-Li Li ; Yong-Xiang Wang ; Hong-Fa Wang
• 刊名：Organometallics
• 出版年：2015
• 出版时间：August 24, 2015
• 年：2015
• 卷：34
• 期：16
• 页码：4147-4157
• 全文大小：570K
• ISSN：1520-6041

文摘

The first [Fe₂SP] model complexes for the active site of [FeFe]-hydrogenases have been prepared. Thus, the 渭-CO-containing complex salt [Et₃NH][(渭-CO)(渭-SCH₂CH₂OH)Fe₂(CO)₆] (m₁) formed from Fe₃(CO)₁₂, HSCH₂CH₂OH, and Et₃N was treated in situ with PCl₃ and PPhCl₂ followed by treatment with Et₃N/DBU to give the all-carbonyl complexes (渭-SCH₂CH₂OPR-渭)Fe₂(CO)₆ (1, R = Cl; 3, Ph), whereas the functional transformation of 1 with PhOH/NaH and CO substitution of 3 with PPh₃ or PPh₂H in the presence of Me₃NO afforded the corresponding complexes (渭-SCH₂CH₂OPOPh-渭)Fe₂(CO)₆ (2) and (渭-SCH₂CH₂OPPh-渭)Fe₂(CO)₅L (4, L = PPh₃; 5, PPh₂H), respectively. Similarly, when complex salt [Et₃NH][(渭-CO)(渭-SC₆H₄OH)Fe₂(CO)₆] (m₄) generated from Fe₃(CO)₁₂, 2-HOC₆H₄SH, and Et₃N was treated in situ with PCl₃ and PPhCl₂ followed by treatment with Et₃N/DBU, the expected all-carbonyl complexes (渭-SC₆H₄OPR-渭)Fe₂(CO)₆ (6, R = Cl; 8, Ph) were produced. In addition, further functional transformation of 6 with MeOH/Et₃N and CO substitution of 8 with t-BuNC in the presence of Me₃NO yielded the corresponding complexes (渭-SC₆H₄OPOMe-渭)Fe₂(CO)₆ (7) and (渭-SC₆H₄OPPh-渭)Fe₂(CO)₅(t-BuNC) (9), respectively. However, it should be noted that when complex salt m₄ was treated with PBr₃ under similar conditions, [(渭-SC₆H₄OPO(CH₂)₄Br-渭]Fe₂(CO)₆ (10) was unexpectedly obtained. While the possible pathways for formation of the unexpected 10 were suggested, all complexes 1鈥?b>10 were characterized by elemental analysis and spectroscopy and for some of them by X-ray crystallography. Interestingly, model complexes 1, 4, and 8 have been found to be catalysts for HOAc proton reduction to H₂ under CV conditions.