The solid- and solution-state structures of 2-nitrosopyridine and its 3- and 4-methyl derivatives
| Autor: | Giuseppe Mele, Mark J. Maidment, Michael B. Hursthouse, Keith G. Orrell, Vladimir Šik, K.M. Abdul Malik, Brian G. Gowenlock, Giuseppe Vasapollo |
|---|---|
| Rok vydání: | 2000 |
| Předmět: | |
| Zdroj: | Journal of the Chemical Society, Perkin Transactions 2. :2280-2286 |
| ISSN: | 1364-5471 1470-1820 |
| DOI: | 10.1039/b004270f |
| Popis: | 2-Nitrosopyridine, 1, 3-methyl-2-nitrosopyridine, 2, and 4-methyl-2-nitrosopyridine, 3, exist in organic solvents as monomer–azodioxy dimer equilibria with the dimers predominating at ambient temperatures. In the case of compounds 1 and 3 only the Z-dimers co-exist with the monomers, whereas for compound 2 both Z- (major) and E- (minor) dimers are present with the monomer. Variable temperature 1H NMR bandshape analysis and 2D-EXSY spectra of 1–3 provided thermodynamic and kinetic data for the dissociation equilibria Z- (or E-) dimer ⇌ 2 monomer, ΔH values being in the range 53–58 kJ mol−1 and ΔG‡ (298.15 K) values in the range 70–82 kJ mol−1. An X-ray crystal structure of 1 identified the compound as a Z-dimeric species with the two pyridine rings twisted by 62.7° and their heterocyclic N atoms pointing towards each other. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|