Characterization of a monocyanide model of FeFe hydrogenases - highlighting the importance of the bridgehead nitrogen for catalysis

被引:21
作者
Esmieu, C. [1 ]
Berggren, G. [1 ]
机构
[1] Uppsala Univ, Dept Chem, Angstrom Lab, Mol Biomimet, S-75120 Uppsala, Sweden
基金
瑞典研究理事会;
关键词
IRON-ONLY HYDROGENASE; ACTIVE-SITE; GENERATION; EVOLUTION; COFACTOR; LIGANDS; ANALOGS;
D O I
10.1039/c6dt02061e
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
An azadithiolate bridged monocyanide derivative [Fe-2(adt)(CO)(5)(CN)](-) of [Fe-2(adt)(CO)(4)(CN)(2)](2-) has been prepared and extensively characterized as a model of the [FeFe]-hydrogenase active site, using a combination of FTIR spectroscopy, electrochemical methods and catalytic assays with chemical reductants. The presence of two basic nitrogen sites opens up multiple protonation pathways, enabling catalytic proton reduction. To our knowledge [Fe-2(adt)(CO)(5)(CN)](-) represents the first example of a cyanide containing [FeFe]-hydrogenase active site mimic capable of catalytic H-2 formation in aqueous media.
引用
收藏
页码:19242 / 19248
页数:7
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