Till Schmidt-Räntsch, Hendrik Verplancke, Annemarie Kehl, Jian Sun, Marina Bennati, Max C. Holthausen, Sven Schneider
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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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