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Tricyanomethane and its Ketenimine Tautomer Generated from Different Precursors and Analyzed in Solution, Argon Matrix, and Single Crystal

Klaus Banert, Madhu Chityala, Manfred Hagedorn, Helmut Beckers, Tony Stüker, Sebastian Riedel, Tobias Rüffer, and Heinrich Lang – 2017

Solutions of azidomethylidenemalononitrile were photolyzed at low temperatures to produce the corresponding 2H‐azirine and tricyanomethane, which were analyzed by low‐temperature NMR spectroscopy. The latter product was also observed after short thermolysis of the azide precursor in solution whereas irradiation of the azide isolated in an argon matrix did not lead to tricyanomethane, but to unequivocal detection of the tautomeric ketenimine by IR spectroscopy for the first time. When the long‐known “aquoethereal” greenish phase generated from potassium tricyanomethanide, dilute sulfuric acid, and diethyl ether was rapidly evaporated and sublimed, a mixture of hydronium tricyanomethanide and tricyanomethane was formed instead of the previously claimed ketenimine tautomer. Under special conditions of sublimation, single crystals of tricyanomethane could be isolated, which enabled the analysis of the molecular structure by X‐ray diffraction.

Titel
Tricyanomethane and its Ketenimine Tautomer Generated from Different Precursors and Analyzed in Solution, Argon Matrix, and Single Crystal
Verfasser
Klaus Banert, Madhu Chityala, Manfred Hagedorn, Helmut Beckers, Tony Stüker, Sebastian Riedel, Tobias Rüffer, and Heinrich Lang
Schlagwörter
Azides, Cyanides, Cyanoform, Ketenimines, Reactive Intermediates
Datum
2017
Erschienen in
Angew. Chem. Int. Ed. 2017, 56, 9582-9586.
Zitierweise
DOI: 10.1002/anie.201704561 (Int. Ed.); 10.1002/ange.201704561
Sprache
eng