New Synthetic Routes to Iron鈥揝ulfur Clusters: Deciphering the Repair Chemistry of [2Fe鈥?S] Clusters from Mononitrosyl Iron Complexes

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• 作者：Jessica Fitzpatrick ; Eunsuk Kim
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：November 16, 2015
• 年：2015
• 卷：54
• 期：22
• 页码：10559-10567
• 全文大小：507K
• ISSN：1520-510X

文摘

The nitrosylation of inorganic protein cofactors, specifically that of [Fe鈥揝] clusters to form iron nitrosyls, plays a number of important roles in biological systems. In some of these cases, it is expected that a repair process reverts the nitrosylated iron species to intact [Fe鈥揝] clusters. The repair of nitrosylated [2Fe鈥?S] cluster, primarily in the form of protein-bound dinitrosyl iron complexes (DNICs), has been observed in vitro and in vivo, but the mechanism of this process remains uncertain. The present work expands upon a previous observation (Fitzpatrick et al. J. Am. Chem. Soc. 2014, 136, 7229) of the ability of mononitrosyl iron complexes (MNICs) to be converted into [2Fe鈥?S] clusters by the addition of nothing other than a cysteine analogue. Herein, each of the critical elementary steps in the cluster repair has been dissected to elucidate the roles of the cysteine analogue. Systematic variations of a cysteine analogue employed in the repair reaction suggest that (i) the bidentate coordination of a cysteine analogue to MNIC promotes NO release from iron, and (ii) deprotonation of the 伪 carbon of the ferric-bound cysteine analogue leads to the C鈥揝 cleavage en route to the formation of [2Fe鈥?S] cluster. The [2Fe鈥?S] cluster bearing a cysteine analogue has also been synthesized from thiolate-bridged iron dimers of the form [Fe₂(渭-SR)₂(SR)₄]^{0/2鈥?/sup>, which implies that such species may be present as intermediates in the cluster repair. In addition to MNICs, mononuclear tetrathiolate ferric or ferrous species have been established as another form of iron from which [2Fe鈥?S] clusters can be generated without need for any other reagent but a cysteine analogue. The results of these experiments bring to light new chemistry of classic coordination complexes and provides further insight into the repair of NO-modified [2Fe鈥?S] clusters.}