Abstract

AbstractThe chromium(III) sensitizer [Cr(ddpd)2]3+ (ddpd=N,N′‐dimethyl‐N,N′‐dipyridine‐2‐ylpyridine‐2,6‐diamine), based on an earth‐abundant metal centre, possesses a unique excited‐state potential‐energy landscape. The very large energy gap between the redox‐active and substitutionally labile 4T2 state and the long‐lived low‐energy 2E spin‐flip state enables a selective, efficient sensitization of triplet dioxygen to give singlet dioxygen. Ultrafast intersystem crossing after the Franck Condon point from the 4T2 to the 2E excited state within 3.5 ps precludes intermolecular electron‐transfer pathways from the ultrashort‐lived excited 4T2 state. This specific excited‐state reactivity enables a selective visible‐light‐induced C−H bond activation of tertiary amines with 1O2 and subsequent trapping with cyanide to yield α‐aminonitriles in good to excellent yields.

Full Text
Paper version not known

Talk to us

Join us for a 30 min session where you can share your feedback and ask us any queries you have

Schedule a call

Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.