Dataset Information

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 ?-bonds (2 2c-2e ????2 3c-2e ????2 2c-2e ?) and one fluxional ?-bond (1 2c-2e ????1 4c-2e ????1 2c-2e ?) in their ground states and transition states, unveiling the universal ??+?? 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 shielding tensors and chemical shifts of the model compound C₈BH₉ are computationally predicted to facilitate future experiments.

SUBMITTER: Ma YY

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

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

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

Ma Yuan-Yuan YY Yan Miao M Li Hai-Ru HR Wu Yan-Bo YB Tian Xin-Xin XX Lu Hai-Gang HG Li Si-Dian SD

Scientific reports 20191119 1

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 ...[more]

PMID: 31745136

Similar Datasets

Project description:Ag16B4O10 has been obtained as a coarse crystalline material via hydrothermal synthesis, and was characterized by X-ray single crystal and powder diffraction, conductivity and magnetic susceptibility measurements, as well as by DFT based theoretical analyses. Neither composition nor crystal structure nor valence electron counts can be fully rationalized by applying known bonding schemes. While the rare cage anion (B4O10)8- is electron precise, and reflects standard bonding properties, the silver ion substructure necessarily has to accommodate eight excess electrons per formula unit, (Ag+)16(B3+)4(O2-)10 × 8e-, rendering the compound sub-valent with respect to silver. However, the phenomena commonly associated with sub-valence metal (partial) structures are not perceptible in this case. Experimentally, the compound has been found to be semiconducting and diamagnetic, ruling out the presence of itinerant electrons; hence the excess electrons have to localize pairwise. However, no pairwise contractions of silver atoms are realized in the structure, thus excluding formation of 2e-2c bonds. Rather, cluster-like aggregates of an approximately tetrahedral shape exist where the Ag-Ag separations are significantly smaller than in elemental silver. The number of these subunits per formula is four, thus matching the required number of sites for pairwise nesting of eight excess electrons. This scenario has been corroborated by computational analyses of the densities of states and electron localization function (ELF), which clearly indicate the presence of an attractor within the shrunken tetrahedral voids in the silver substructure. However, one bonding electron pair of s and p type skeleton electrons per cluster unit is extremely low, and the significant propensity to form and the thermal stability of the title compound suggest d10-d10 bonding interactions to strengthen the inter-cluster bonding in a synergistic fashion. With the present state of knowledge, such a particular bonding pattern appears to be a singular feature of the oxide chemistry of silver; however, as indicated by analogous findings in related silver oxides, it is evolving as a general one.

Dataset Information

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

Publications

Probing the Fluxional Bonding Nature of Rapid Cope rearrangements in Bullvalene C<sub>10</sub>H<sub>10</sub> and Its Analogs C<sub>8</sub>H<sub>8</sub>, C<sub>9</sub>H<sub>10</sub>, and C<sub>8</sub>BH<sub>9</sub>.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure