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- W2023766090 abstract "B/N-Heterocyclen mit B2N3-Fünfring-Gerüst enthalten 6 π-Elektronen, entstehen bei Umsetzung bifunktioneller Borverbindungen RBX2 mit Monoalkylhydrazinen bevorzugt und sind nach NMR-Untersuchungen planar. Demgegenüber weisen Tetraaza-dibora-cyclohexan-Derivate RB(NR–NR)2BR mit 8 πN-Elektronen eine „Twist”︁-Konformation auf. – Einelektronen-Oxidation der isomeren Fünfring- und Sechsring-B/N-Heterocyclen R2N–N(BR–NR–)2 und RB(NR–NR)2BR mit A1C13 in H2CC12 führt jeweils zum dunkelblauen, bei Raumtemperatur stabilen Radikalkation RB(NR–NR)2BR⊕, das als vermutlich planares 7 π-Elektronensystem mit Benzol-Radikalanionen iso-π-elektronisch ist. Sein hochaufgelöstes und durch Simulation sowie ENDOR-Messungen zugeordnetes ESR-Spektrum zeigt als Sätze äquivalenter Kerne 4N, 12H und 2B. Im Einklang mit MO-Argumenten konzentriert sich die Spindichte überwiegend an den N-Atomen, die B-Atome liegen in π-Knotenflächen, und die NR–NR⊕-Brücken sind eingeebnet. Contributions to the Chemistry of Boron, C Radical Ions, XXXI. NMR and ESR Spectroscopic Investigations on Five- and Six-membered B/N-Heterocycles3) B/N-Heterocycles with a B2N3, ring skeleton contain 6 π electrons, form preferentially on reaction of bifunctional boron compounds RBX2 with monoalkylhydrazines, and possess planar structures according to NMR spectroscopic investigations. In contrast, tetraazadiboracyclohexane derivatives RB(NR–NR)2BR with 8 π electrons exhibit a twist conformation. – One-electron oxidation of the isomeric five- and six-membered B/N-heterocycles R2N–N(BR–NR–)2 and RB(NR-NR)2, BR using A1C13 in H2CCl2 yield each the dark-blue, thermodynamically favored radical cation RB(NR–NR)2BR⊕, which as a presumably planar 7 π-electron system is iso-π-electronic to benzene radical anions. Its high-resolution ESR spectrum has been assigned by simulation as well as ENDOR measurements, and shows as sets of equivalent nuclei 4N, 12H, and 2 B. In accord with MO arguments the spin density concentrates predominantly on the nitrogen atoms, while the boron atoms are located in π-nodal planes and the NR–NR⊕-bridges have been levelled." @default.
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- W2023766090 title "Beiträge zur Chemie des Bors, C. Radikalionen, XXXI. NMR‐ und ESR‐spektroskopische Untersuchungen zur Isomerisierung von Fünfring‐ und Sechsring‐B/N‐Heterocyclen" @default.
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- W2023766090 doi "https://doi.org/10.1002/cber.19791120718" @default.
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