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C=C Dissociative Imination of Styrenes by a Photogenerated Metallonitrene
Till Schmidt-Räntsch1, Hendrik Verplancke2, Annemarie Kehl3,4
1Institut für Anorganische Chemie and International Center for Advanced Studies of Energy Conversion, Georg-August-Universität Göttingen, Tammannstraße 4, 37077 Göttingen, Germany.
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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