C=C Dissociative Imination of Styrenes by a Photogenerated Metallonitrene.

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=CH₂) 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 N₂. The resulting platinum(I) complex initiates a radical chain mechanism via a dinuclear radical-bridged species (Pt^II-CH₂CHPhN^•-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 nucl

SUBMITTER: Schmidt-Rantsch T 

PROVIDER: S-EPMC11423323 | biostudies-literature | 2024 Sep

REPOSITORIES: biostudies-literature