Impact of the macrocyclic structure and dynamic solvent effect on the reactivity of a localised singlet diradicaloid with π-single bonding character.

ABSTRACT: Localised singlet diradicals are key intermediates in bond homolysis processes. Generally, these highly reactive species undergo radical-radical coupling reaction immediately after their generation. Therefore, their short-lived character hampers experimental investigations of their nature. In this study, we implemented the new concept of "stretch effect" to access a kinetically stabilised singlet diradicaloid. To this end, a macrocyclic structure was computationally designed to enable the experimental examination of a singlet diradicaloid with π-single bonding character. The kinetically stabilised diradicaloid exhibited a low carbon-carbon coupling reaction rate of 6.4 × 10³ s^-1 (155.9 μs), approximately 11 and 1000 times slower than those of the first generation of m

SUBMITTER: Wang Z 

PROVIDER: S-EPMC8179019 | biostudies-literature | 2020 Nov

REPOSITORIES: biostudies-literature