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(II)-N=CHPh) and formimido (Pt(II)-N=CH(2)) complexes as the main products. Spectroscopic and quantum chemical examinations support a mechanism that commences with the decay of the metallonitrene photoproduct (Pt(II)-N) via bimolecular coupling and nitrogen loss as N(2). The resulting platinum(I) complex initiates a radical chain mechanism via a dinuclear radical-bridged species (Pt(II)-CH(2)CHPhN(•)-Pt(II)) as a direct precursor to C-C scission. The preference for the Pt(I) mediated route over styrene aziridination is attributed to the distinct nucleophilicity of the triplet metallonitrene.