An S-Oxygenated [NiFe] Complex Modelling Sulfenate Intermediates of an O2-Tolerant Hydrogenase
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- 作者：Nils J. Lindenmaier ; Stefan Wahlefeld ; Dr. Eckhard Bill ; Dr. Tibor Szilvá ; si ; Christopher Eberle ; Dr. Shenglai Yao ; Prof. Dr. Peter Hildebrandt ; Dr. Marius Horch ; Dr. Ingo Zebger and Prof. Dr. Matthias Driess
- 刊名：Angewandte Chemie International Edition
- 出版年：2017
- 出版时间：February 13, 2017
- 年：2017
- 卷：56
- 期：8
- 页码：2208-2211
- 全文大小：1367K
- ISSN：1521-3773
文摘
To understand the molecular details of O2-tolerant hydrogen cycling by a soluble NAD+-reducing [NiFe] hydrogenase, we herein present the first bioinspired heterobimetallic S-oxygenated [NiFe] complex as a structural and vibrational spectroscopic model for the oxygen-inhibited [NiFe] active site. This compound and its non-S-oxygenated congener were fully characterized, and their electronic structures were elucidated in a combined experimental and theoretical study with emphasis on the bridging sulfenato moiety. Based on the vibrational spectroscopic properties of these complexes, we also propose novel strategies for exploring S-oxygenated intermediates in hydrogenases and similar enzymes.