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2,6-Diazasemibullvalenes: Synthesis, Structural Characterization, and Theoretical Analysis

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The Chemistry of Zirconacycles and 2,6-Diazasemibullvalenes

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Abstract

Efficient one-pot synthesis and isolation of a series of NSBVs were developed by oxidant-induced C–N bond formation. For the first time, the single-crystal structure of an NSBV (5-1a) was determined and the molecule showed a localized structure. The C-symmetrical structure of 5-1a in solution along with line broadening of the NMR signal at −110 °C indicates an extremely low barrier of the rapid degenerate aza-Cope rearrangement. DFT calculations at B3LYP/6-31G* level show that 5-1a should be the predominant form in the gas or condensed phase; however, the existence of the homoaromatic 5-1a deloc is highly possible. The activation barrier ΔG‡ was determined to be 4.4 kcal/mol by line shape analysis of low-temperature 13C NMR spectra, comparable with 2.1 kcal/mol calculated value.

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  1. College of Chemistry and Molecular Engineering, Peking University, Beijing, China

    Shaoguang Zhang

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Correspondence to Shaoguang Zhang .

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Zhang, S. (2015). 2,6-Diazasemibullvalenes: Synthesis, Structural Characterization, and Theoretical Analysis. In: The Chemistry of Zirconacycles and 2,6-Diazasemibullvalenes. Springer Theses. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-662-45021-5_5

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