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  • Title: Spin-Spin Coupling Between Two meta-Benzyne Moieties In a Quinolinium Tetraradical Cation Increases Their Reactivities.
    Author: Kotha RR, Yerabolu R, Ding D, Szalwinski L, Ma X, Wittrig A, Kong J, Nash JJ, Kenttämaa HI.
    Journal: Chemistry; 2019 Mar 21; 25(17):4472-4477. PubMed ID: 30648302.
    Abstract:
    The reactivity of a carbon-centered σ,σ,σ,σ-type singlet-ground-state tetraradical containing two meta-benzyne moieties was examined in the gas phase. Surprisingly, the tetraradical showed higher reactivity than its individual meta-benzyne counterparts. The reactivity of meta-benzynes is controlled by their (calculated) distortion energy ΔE2.3 , singlet-triplet spitting ΔES-T , and electron affinity (EA2.3 ) of the meta-benzyne moiety at the transition state geometry for hydrogen-atom abstraction reactions. The addition of a second meta-benzyne moiety to a meta-benzyne does not significantly change EA2.3 . However, ΔE2.3 is substantially decreased for both meta-benzyne moieties in the tetraradical, and this explains their higher reactivities. The decrease in ΔE2.3 for each meta-benzyne moiety in the tetraradical is rationalized by stabilizing spin-spin coupling between one radical site in each meta-benzyne moiety. Therefore, spin-spin coupling between the meta-benzyne moieties in this tetraradical increases its reactivity, whereas spin-spin coupling within each meta-benzyne moiety decreases its reactivity.
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