A Nitrogenase Cluster Model [Fe8S6O] with an Oxygen Unsymmetrically Bridging Two Proto-Fe4S3 Cubes: Relevancy to the Substrate Binding Mode of the FeMo Cofactor

作者：Ohta Shun; Ohki Yasuhiro; Hashimoto Takayoshi; Cramer Roger E; Tatsumi Kazuyuki^*

来源：Inorganic Chemistry, 2012, 51(21): 11217-11219.

DOI：10.1021/ic301348f

An oxygen-encapsulated iron sulfido cluster, [(DmpS)Fe4S3O][(DmpS)Fe4S3](mu-SDmp)(2)(mu-OCPh3) (2; Dmp = 2,6-(mesityl)(2)C6H3), has been synthesized by the reaction of the preformed dinuclear iron thiolate/alkoxide [(Ph3CO)Fe](2)(mu-SDmp)(2) (1) with 1/8 S-8 and 1/4 H2O in toluene. In the [Fe8S6O] core, the oxygen atom bridges unsymmetrically two incomplete Fe4S3 cubes, and two coordinatively unsaturated iron atoms are weakly bound to mesityl rings. Relevance of the cluster structure of 2 to the nitrogenase FeMo cofactor and its substrate binding mode is discussed.

• 出版日期2012-11-5