Characterization of a diferrous terminal hydride mechanistically relevant to the Fe-only hydrogenases
Characterization of a diferrous terminal hydride mechanistically relevant to the Fe-only hydrogenases
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DOI：
10.1021/ja055475a
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发表时间：
2005-11-23
影响因子：
15
通讯作者：
Wilson, SR
中科院分区：
文献类型：
--
作者：
van der Vlugt, JI;Rauchfuss, TB;Wilson, SR
用氢化物给体试剂还原二硫羟酸二亚铁络合物得到了先前难以理解的末端二亚铁氢化物[Fe 2（edt）（μ-CO）（H）（CO）（PMe 3）4] PF 6（edt = S2 C2 H4）的第一个实例。晶体学表征表明，该模型包含一个不对称的半桥CO反式到一个末端的反式，如D中的Hred状态所示。脱硫酶该模型与质子反应产生H2，并通过分子内过程重排为同分异构的μ-双氢异构体，该异构体对质子不起反应。
Reduction of diferrous dithiolato complexes with hydride donor reagents affords the first example of the previously elusive terminal diferrous hydride, [Fe2(edt)(μ-CO)(H)(CO)(PMe3)4]PF6(edt = S2C2H4). Crystallographic characterization shows that this model contains an asymmetrical semi-bridging CO trans to a terminal hydrido, as indicated in the Hredstate in theD. desulfuricansenzyme. The model reacts with protons to yield H2and rearranges via an intramolecular process to the isomeric μ-hydrido isomer, which is unreactive toward protons.