Till Schmidt-Räntsch, Hendrik Verplancke, Annemarie Kehl, Jian Sun, Marina Bennati, Max C. Holthausen, Sven Schneider
{"title":"C═C Dissociative Imination of Styrenes by a Photogenerated Metallonitrene","authors":"Till Schmidt-Räntsch, Hendrik Verplancke, Annemarie Kehl, Jian Sun, Marina Bennati, Max C. Holthausen, Sven Schneider","doi":"10.1021/jacsau.4c00571","DOIUrl":null,"url":null,"abstract":"Photolysis of a platinum(II) azide complex in the presence of styrenes enables C═C double bond cleavage upon dissociative olefin imination to aldimido (Pt<sup>II</sup>–N═CHPh) and formimido (Pt<sup>II</sup>–N═CH<sub>2</sub>) complexes as the main products. Spectroscopic and quantum chemical examinations support a mechanism that commences with the decay of the metallonitrene photoproduct (Pt<sup>II</sup>–N) via bimolecular coupling and nitrogen loss as N<sub>2</sub>. The resulting platinum(I) complex initiates a radical chain mechanism via a dinuclear radical-bridged species (Pt<sup>II</sup>–CH<sub>2</sub>CHPhN<sup>•</sup>–Pt<sup>II</sup>) as a direct precursor to C–C scission. The preference for the Pt<sup>I</sup> mediated route over styrene aziridination is attributed to the distinct nucleophilicity of the triplet metallonitrene.","PeriodicalId":14799,"journal":{"name":"JACS Au","volume":null,"pages":null},"PeriodicalIF":0.0000,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"JACS Au","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1021/jacsau.4c00571","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 0
Abstract
Photolysis of a platinum(II) azide complex in the presence of styrenes enables C═C double bond cleavage upon dissociative olefin imination to aldimido (PtII–N═CHPh) and formimido (PtII–N═CH2) complexes as the main products. Spectroscopic and quantum chemical examinations support a mechanism that commences with the decay of the metallonitrene photoproduct (PtII–N) via bimolecular coupling and nitrogen loss as N2. The resulting platinum(I) complex initiates a radical chain mechanism via a dinuclear radical-bridged species (PtII–CH2CHPhN•–PtII) as a direct precursor to C–C scission. The preference for the PtI mediated route over styrene aziridination is attributed to the distinct nucleophilicity of the triplet metallonitrene.
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