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 (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.
Authors
- Annemarie Kehl (ORCID: https://orcid.org/0000-0002-6105-8252)
- Jian Sun (ORCID: https://orcid.org/0000-0001-9397-3191)
- Marina Bennati (ORCID: https://orcid.org/0000-0001-6784-7845)
- Till Schmidt‐Räntsch (ORCID: https://orcid.org/0000-0003-4803-7788)
- Sven Schneider (ORCID: https://orcid.org/0000-0002-8432-7830)
- Max C. Holthausen (ORCID: https://orcid.org/0000-0001-7283-8329)
- Hendrik Verplancke (ORCID: https://orcid.org/0000-0002-3587-845X)
Institutions
- Goethe University Frankfurt (DE)
- Max Planck Institute for Multidisciplinary Sciences (DE)
- University of Göttingen (DE)
Publication Details
- Journal
- JACS Au
- Published
- 2024-09-03
- DOI
- https://doi.org/10.1021/jacsau.4c00571
- Citations
- 5
- Primary Topic
- Synthesis and Catalytic Reactions
- Type
- article
- Field-Weighted Citation Impact
- 1.25
Funders
- Deutsche Forschungsgemeinschaft
- Georg-August-Universität Göttingen
- China Scholarship Council