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扩展[铁铁]氢化酶活性位点模型的基序：Fe2(NR)2(CO)6-xLx物种的质子化

Extending the motif of the [FeFe]-hydrogenase active site models: protonation of Fe2(NR)2(CO)6-xLx species.

作者信息

Volkers Phillip I, Rauchfuss Thomas B

机构信息

Department of Chemistry, University of Illinois, 601 S. Goodwin Ave., Urbana, IL 61801, USA.

出版信息

J Inorg Biochem. 2007 Nov;101(11-12):1748-51. doi: 10.1016/j.jinorgbio.2007.05.005. Epub 2007 May 24.

DOI:10.1016/j.jinorgbio.2007.05.005
PMID:17606299
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC2440487/
Abstract

Studies on diiron dithiolato complexes have proven fruitful for modeling the active site of the [FeFe]-hydrogenases. Here we present a departure from the classical Fe(2)S(2) motif by examining the viability of Fe(2)N(2) butterfly compounds as functional models for the diiron active site of [FeFe]-hydrogenases. Derivatization of Fe(2)(BC)(CO)(6) (1, BC=benzo-[c]-cinnoline) with PMe(3) affords Fe(2)(BC)(CO)(4)(PMe(3))(2), which subsequently undergoes protonation at the Fe-Fe bond. The hydride [(mu-H)Fe(2)(BC)(CO)(4)(PMe(3))(2)]PF(6) was characterized crystallographically as the C(2v) isomer. It represents a rare example of a hydrido diiron complex that exists as observable isomers, depending on the location of the phosphine ligands--diapical and apical-basal. This hydride catalyzes the electrochemical reduction of protons.

摘要

对二铁二硫醇配合物的研究已证明在模拟[FeFe]-氢化酶的活性位点方面卓有成效。在此，我们通过研究Fe(2)N(2)蝶形化合物作为[FeFe]-氢化酶二铁活性位点功能模型的可行性，偏离了经典的Fe(2)S(2)基序。用PMe(3)对Fe(2)(BC)(CO)(6)（1，BC = 苯并[c]噌啉）进行衍生化得到Fe(2)(BC)(CO)(4)(PMe(3))(2)，其随后在Fe-Fe键处发生质子化。氢化物[(μ-H)Fe(2)(BC)(CO)(4)(PMe(3))(2)]PF(6)经晶体学表征为C(2v)异构体。它代表了一种罕见的氢化二铁配合物实例，根据膦配体的位置（双顶端和顶端-基部）以可观察到的异构体形式存在。这种氢化物催化质子的电化学还原。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/49b2/2440487/489745d344ff/nihms50844f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/49b2/2440487/f6cf6f65591a/nihms50844f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/49b2/2440487/5f84d8442dfd/nihms50844f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/49b2/2440487/9f79cf19cebf/nihms50844f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/49b2/2440487/489745d344ff/nihms50844f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/49b2/2440487/f6cf6f65591a/nihms50844f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/49b2/2440487/5f84d8442dfd/nihms50844f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/49b2/2440487/9f79cf19cebf/nihms50844f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/49b2/2440487/489745d344ff/nihms50844f4.jpg

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本文引用的文献

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Organometallics. 2007;26(8):1907-1911. doi: 10.1021/om0611150.
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Carbene-pyridine chelating 2Fe2S hydrogenase model complexes as highly active catalysts for the electrochemical reduction of protons from weak acid (HOAc).卡宾-吡啶螯合的2Fe2S氢化酶模型配合物作为从弱酸（HOAc）电化学还原质子的高活性催化剂。
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Fe-S complexes containing five-membered heterocycles: novel models for the active site of hydrogenases with unusual low reduction potential.含五元杂环的铁硫配合物：具有异常低还原电位的氢化酶活性位点的新型模型。
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A biomimetic model for the active site of iron-only hydrogenases covalently bonded to a porphyrin photosensitizer.一种与卟啉光敏剂共价结合的仅含Fe氢化酶活性位点的仿生模型。
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