文章基本信息

标题：A model for the CO-inhibited form of [NiFe] hydrogenase: synthesis of (CO)3Fe(μ-StBu)3Ni{SC6H3-2,6-(mesityl)2} and reversible CO addition at the Ni site
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作者：Yasuhiro Ohki ; Kazunari Yasumura ; Masaru Ando 等
期刊名称：Proceedings of the National Academy of Sciences
印刷版ISSN：0027-8424
电子版ISSN：1091-6490
出版年度：2010
卷号：107
期号：9
页码：3994-3997
DOI：10.1073/pnas.0913399107
语种：English
出版社：The National Academy of Sciences of the United States of America
摘要：A [NiFe] hydrogenase model compound having a distorted trigonal-pyramidal nickel center, (CO)3Fe({micro}-StBu)3Ni(SDmp), 1 (Dmp = C6H3-2,6-(mesityl)2), was synthesized from the reaction of the tetranuclear Fe-Ni-Ni-Fe complex [(CO)3Fe({micro}-StBu)3Ni]2({micro}-Br)2, 2 with NaSDmp at -40 {degrees}C. The nickel site of complex 1 was found to add CO or CNtBu at -40 {degrees}C to give (CO)3Fe(StBu)({micro}-StBu)2Ni(CO)(SDmp), 3, or (CO)3Fe(StBu)({micro}-StBu)2Ni(CNtBu)(SDmp), 4, respectively. One of the CO bands of 3, appearing at 2055 cm-1 in the infrared spectrum, was assigned as the Ni-CO band, and this frequency is comparable to those observed for the CO-inhibited forms of [NiFe] hydrogenase. Like the CO-inhibited forms of [NiFe] hydrogenase, the coordination of CO at the nickel site of 1 is reversible, while the CNtBu adduct 4 is more robust.
关键词：iron ; nickel ; thiolates