FigsharePub Date : 2023-01-23DOI: 10.1021/jacs.2c13126.s001
AlexandraC. Brown (6499649), Daniel L. M. Suess (7255208)
{"title":"An Open-Cuboidal [Fe<sub>3</sub>S<sub>4</sub>] ClusternCharacterized in Both Biologically Relevant Redox States","authors":"AlexandraC. Brown (6499649), Daniel L. M. Suess (7255208)","doi":"10.1021/jacs.2c13126.s001","DOIUrl":"https://doi.org/10.1021/jacs.2c13126.s001","url":null,"abstract":"Synthetic analogues of the three common types of Fe–Snclustersnfound in biologydiamond-core [Fe<sub>2</sub>S<sub>2</sub>]nclusters, open-cuboidal [Fe<sub>3</sub>S<sub>4</sub>] clusters, andncuboidal [Fe<sub>4</sub>S<sub>4</sub>] clustershave been reportednin each biologically relevant redox state with one exception: thenopen-cuboidal [Fe<sub>3</sub>S<sub>4</sub>]<sup>+</sup> cluster. Here,nwe describe the synthesis and characterization of an open-cuboidaln[Fe<sub>3</sub>S<sub>4</sub>] cluster in both biologically relevantnredox states: [Fe<sub>3</sub>S<sub>4</sub>]<sup>+</sup> and [Fe<sub>3</sub>S<sub>4</sub>]<sup>0</sup>. Like their biological counterparts,nthe oxidized cluster has a spin-canted, <i>S</i> = <sup>1</sup>/<sub>2</sub> ground state, and the reduced cluster has an <i>S</i> = 2 ground state. Structural analysis reveals that then[Fe<sub>3</sub>S<sub>4</sub>] core undergoes substantial contractionnupon oxidation, in contrast to the minimal structural changes observednfor the only [Fe<sub>3</sub>S<sub>4</sub>] protein for which high-resolutionnstructures are available in both redox states (<i>Azotobacternvinelandii</i> ferredoxin I; <i>Av</i> FdI). This differencenbetween the synthetic models and <i>Av</i> FdI is discussednin the context of electron transfer by [Fe<sub>3</sub>S<sub>4</sub>] proteins.","PeriodicalId":522654,"journal":{"name":"Figshare","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147901062","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}