Unimolecular net heterolysis of symmetric and homopolar σ-bonds.

ABSTRACT: The unimolecular heterolysis of covalent σ-bonds is integral to many chemical transformations, including S_N1-, E1- and 1,2-migration reactions. To a first approximation, the unequal redistribution of electron density during bond heterolysis is governed by the difference in polarity of the two departing bonding partners^1-3. This means that if a σ-bond consists of two identical groups (that is, symmetric σ-bonds), its unimolecular fission from the S₀, S₁, or T₁ states only occurs homolytically after thermal or photochemical activation^1-7. To force symmetric σ-bonds into heterolytic manifolds, co-activation by bimolecular noncovalent interactions is necessary⁴. These tactics are only applicable to σ-bond constituents

SUBMITTER: Tiefel AF 

PROVIDER: S-EPMC11324518 | biostudies-literature | 2024 Aug

REPOSITORIES: biostudies-literature