Methoxyphenyl‐Functionalized Diiron Azadithiolates as Models for the Active Site of Fe‐Only Hydrogenases: Synthesis, Structures, and Biomimetic H2 Evolution
Methoxyphenyl‐Functionalized Diiron Azadithiolates as Models for the Active Site of Fe‐Only Hydrogenases: Synthesis, Structures, and Biomimetic H2 Evolution
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DOI：
10.1002/ejic.200600242
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发表时间：
2006-08
影响因子：
2.3
通讯作者：
Li-Cheng Song;Jian-Hua Ge;Xiao-Guang Zhang;Yang Liu;Q. Hu
中科院分区：
文献类型：
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作者：
Li-Cheng Song;Jian-Hua Ge;Xiao-Guang Zhang;Yang Liu;Q. Hu
A series of methoxyphenyl-functionalized diiron azadithiolate (ADT) complexes, [{(μ-SCH2)2N(C6H4OMe-p)}Fe2(CO)5L] [L = CO (2); PPh3 (3); PPh2H (4)] and [{(μ-SCH2)2N(C6H4OMe-p)}Fe2(CO)4(CN)2][Et4N]2 (5) as the active site models of Fe-only hydrogenases has been investigated. While model 2 was prepared in 67 % yield by a condensation reaction of N,N-bis(chloromethyl)-p-methoxyaniline (1) with [(μ-LiS)2Fe2(CO)6], models 3–5 were prepared in 49–75 % yields by a CO substitution reaction of 2 with PPh3, PPh2H, or Et4NCN, respectively. The X-ray crystal structures of 2 and 3 revealed that the methoxyphenyl substituent is attached to the N atom by an axial bond and the nitrogen lone electron pair in an equatorial position. On the basis of cyclic voltammetric studies of 2 and 4, it was found that 2 is a catalyst for proton reduction, and an EECC mechanism is proposed for such electrocatalytic H2 production catalyzed by the ADT-type models. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
