Probing the Fluxional Bonding Nature of Rapid Cope rearrangements in Bullvalene C₁₀H₁₀ and Its Analogs C₈H₈, C₉H₁₀, and C₈BH₉.

ABSTRACT: Bullvalene C₁₀H₁₀ and its analogs semibullvalene C₈H₈, barbaralane C₉H₁₀, and 9-Borabarbaralane C₈BH₉ are prototypical fluxional molecules with rapid Cope rearrangements at finite temperatures. Detailed bonding analyses performed in this work reveal the existence of two fluxional π-bonds (2 2c-2e π → 2 3c-2e π → 2 2c-2e π) and one fluxional σ-bond (1 2c-2e σ → 1 4c-2e σ → 1 2c-2e σ) in their ground states and transition states, unveiling the universal π + σ double fluxional bonding nature of these fluctuating cage-like species. The highest occupied natural bond orbitals (HONBOs) turn out to be typical fluxional bonds dominating the dynamics of the systems. The ¹³C-NMR and ¹H-NMR sh

SUBMITTER: Ma YY 

PROVIDER: S-EPMC6864245 | biostudies-literature | 2019 Nov

REPOSITORIES: biostudies-literature