Till Schmidt-Räntsch, Hendrik Verplancke, Annemarie Kehl, Jian Sun, Marina Bennati, Max C. Holthausen* and Sven Schneider*,
{"title":"光生茂金属烯对苯乙烯的 C═C 解离氨基化作用","authors":"Till Schmidt-Räntsch, Hendrik Verplancke, Annemarie Kehl, Jian Sun, Marina Bennati, Max C. Holthausen* and Sven Schneider*, ","doi":"10.1021/jacsau.4c0057110.1021/jacsau.4c00571","DOIUrl":null,"url":null,"abstract":"<p >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.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"4 9","pages":"3421–3426 3421–3426"},"PeriodicalIF":8.5000,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.4c00571","citationCount":"0","resultStr":"{\"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* and Sven Schneider*, \",\"doi\":\"10.1021/jacsau.4c0057110.1021/jacsau.4c00571\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >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.</p>\",\"PeriodicalId\":94060,\"journal\":{\"name\":\"JACS Au\",\"volume\":\"4 9\",\"pages\":\"3421–3426 3421–3426\"},\"PeriodicalIF\":8.5000,\"publicationDate\":\"2024-09-03\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.acs.org/doi/epdf/10.1021/jacsau.4c00571\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"JACS Au\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/jacsau.4c00571\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"JACS Au","FirstCategoryId":"1085","ListUrlMain":"https://pubs.acs.org/doi/10.1021/jacsau.4c00571","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
C═C Dissociative Imination of Styrenes by a Photogenerated Metallonitrene
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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