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New insights on the bridge carbon–carbon bond in propellanes: A theoretical study based on the analysis of the electron localization function by Victor Polo; Juan Andres; Bernard Silvi is a Chemistry article available to read on EtoBox.

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## Abstract The nature of the bonding between bridgehead carbon atoms (Ca, Ca′) as well as the ring strain in a family of 10 propellanes formed by three‐, four‐, or five‐member rings: [1.1.1] (I), [2.1.1] (II), [3.1.1] (III), [2.2.1] (IV), [3.2.1] (V), [2.2.2] (VI), [3.3.1] (VII), [3.2.2] (VIII), [3.3.2] (IX), and [3.3.3] (X) are studied by means of the electron localization function (ELF) at the DFT level (B3LYP/cc‐pVTZ). The ELF analysis of smaller propellanes (I, II, and III) reveals the coexistence of two resonance forms: one with a nonbonding electron pair partially delocalized between Ca and Ca′ atoms outside the cage (ionic) and the other with a bridge bond between the same atoms (covalent). The weights of each form are calculated according to the ELF‐basin populations, yielding 94, 88, and 53% for the ionic structure of I, II, and III, respectively, while larger propellanes (IV–X) present only the covalent form. The question of the s‐character of the bridge bond is addressed by dissecting the bridge‐bond ELF basin into the molecular orbital contributions. Finally, σ‐aromaticity associated to surface electron delocalization has been analyzed by means of nucleus‐independent c

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Author

Victor Polo; Juan Andres; Bernard Silvi

Publisher

John Wiley and Sons; Wiley (John Wiley & Sons); John Wiley & Sons Inc.; Wiley (ISSN 0192-8651)

Published

2007

Language

EN

Field

Chemistry (Physical Sciences)