Pronounced electronic modulation of geometrically-regulated metalloenediyne cyclization

Le résumé fourni par la source

). Computational interrogation of the aryl phosphine metalloenediynes 3a-3e reveals that the origin of this precise electronic control derives from electronic withdrawing group-mediated alkyne carbon polarization that amplifies coulombic repulsion increasing the cyclization barrier height. Additionally, mixing between the in-plane π-orbitals and the phosphine aryl ring system is pronounced for complexes with electron donating substituents which stabilizes the developing C-C bond and lowers the activation barrier. This π-orbital mixing is negligible however, for complexes with electron withdrawing substituents due to an energetic mismatch of the orbital systems. Overall, this work demonstrates that for geometrically rigid frameworks, even remote enediyne functionalization can have pronounced effects on activation barrier.

Ce résumé expose les affirmations des auteurs. BNTIC ne l’interprète pas comme une validation indépendante des résultats.