Struktur, Dipolmoment und <sup>14</sup>N-Kernquadrupolkopplungskonstante des Acetonitril-N-Oxids aus dem Mikrowellenspektrum / Structure, Dipole Moment and <sup>14</sup>N-Nuclear Quadrupole Coupling Constant of Acetonitrile-N-Oxide from the Microwave Spectrum

Bodenseh, H. K.; Morgenstern, Klaus

doi:10.1515/zna-1970-0126

Cited by 22 publications

(2 citation statements)

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“…Unfortunately, few previous experimental and theoretical works attend to low stable isomers MC, FULM, and AOX. [7][8][9][10][11][12][13][14] To our knowledge nothing has been said concerning MCON. Sakaizumi et al 7 first analyzed the methyl cyanate microwave spectrum and estimated the dipole moment to be 4.26 (46) D (µ a = 4.07 (6); µ b = 1.24 (40) J ′′ = 10-35 and K a ′′ = 0-13) was recorded deriving spectroscopic constants reproducing the spectrum close to the experimental uncertainty.…”

Section: Introductionmentioning

confidence: 99%

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Structural and spectroscopic characterization of methyl isocyanate, methyl cyanate, methyl fulminate, and acetonitrile N-oxide using highly correlated ab initio methods

Dalbouha

Senent

Komiha

et al. 2016

The Journal of Chemical Physics

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Various astrophysical relevant molecules obeying the empirical formula CHNO are characterized using explicitly correlated coupled cluster methods (CCSD(T)-F12). Rotational and rovibrational parameters are provided for four isomers: methyl isocyanate (CHNCO), methyl cyanate (CHOCN), methyl fulminate (CHONC), and acetonitrile N-oxide (CHCNO). A CHCON transition state is inspected. A variational procedure is employed to explore the far infrared region because some species present non-rigidity. Second order perturbation theory is used for the determination of anharmonic frequencies, rovibrational constants, and to predict Fermi resonances. Three species, methyl cyanate, methyl fulminate, and CHCON, show a unique methyl torsion hindered by energy barriers. In methyl isocyanate, the methyl group barrier is so low that the internal top can be considered a free rotor. On the other hand, acetonitrile N-oxide presents a linear skeleton, C symmetry, and free internal rotation. Its equilibrium geometry depends strongly on electron correlation. The remaining isomers present a bend skeleton. Divergences between theoretical rotational constants and previous parameters fitted from observed lines for methyl isocyanate are discussed on the basis of the relevant rovibrational interaction and the quasi-linearity of the molecular skeleton.

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Section: Introductionmentioning

confidence: 99%

“…The AOX microwave spectrum recorded in the ground state and in the two first excited bending states 12,13 is consistent with a symmetric top. [10][11][12][13] AOX was obtained as products of reactions of oxygen atoms and acetonitrile in solid argon. 14 Methyl isocyanate is the isomer which has inspired more interest.…”

Section: Introductionmentioning

confidence: 99%

Structural and spectroscopic characterization of methyl isocyanate, methyl cyanate, methyl fulminate, and acetonitrile N-oxide using highly correlated ab initio methods

Dalbouha

Senent

Komiha

et al. 2016

The Journal of Chemical Physics

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Nitrilimine: von der Charakterisierung in Matrix zu stabilen Verbindungen

Bertrand

Wentrup

1994

Angewandte Chemie

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Aus dem Konzept der 1,3‐Dipolaren Cycloaddition, das zum größten Teil auf Rolf Huisgen und seine Schule in München zurückgeht und das aus den späten fünfziger Jahren stammt, hat sich eine der vielseitigsten Methoden für den Aufbau fünfgliedriger Heterocyclen entwickelt. Obwohl zuerst nur als labile Zwischenstufen bekannt, standen Nitrilimine im Mittelpunkt mechanistischer Untersuchungen dieser Art von Cycloadditionen, wie Hunderte von Publikationen aus den sechziger und siebziger Jahren zeigen. Spektroskopisch nachgewiesen sowohl bei niedrigen Temperaturen als auch in der Gasphase wurden diese Verbindungen in den frühen achtziger Jahren; 1988 schließlich wurde das erste kristalline Nitrilimin vorgestellt. Die ungewöhnlichen, durch Röntgenbeugung ermittelten Strukturen und auch die Leichtigkeit, mit der diese Verbindungen umlagern, haben das Zusammenspiel von Experiment und Theorie gefördert. Die Geschichte der Nitrilimine von der Charakterisierung in Matrix bis zu stabilen Verbindungen veranschaulicht in hervorragender Weise die Rolle, die Hauptgruppenelemente in der Organischen Chemie spielen könen.

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Nitrile Imines: From Matrix Characterization to Stable Compounds

Bertrand

Wentrup

1994

Angew. Chem. Int. Ed. Engl.

119

100

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The concept of 1,3‐dipolar cycloaddition was developed, starting in the late 1950s, largely by Rolf Huisgen and his students in Munich, and it has led to one of the most versatile methods for the construction of five‐membered ring heterocycles. Although first known only as transient intermediates, nitrile imines have been at the heart of mechanistic studies of this type of cycloaddition reactions. Hundreds of mechanistic papers appeared in 1960s and 1970s; reliable spectroscopic observations were achieved in the early 1980s both at low temperatures and in the gas phase; finally, the first crystalline nitrile imine was reported in 1988. The unusual structures found by X‐ray analyses as well as the facile rearrangements observed experimentally have fostered a new interplay between experiment and theory. The story of nitrile imines, from matrix characterization to stable compounds, nicely illustrates the role that main group elements can play in organic chemistry.

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Struktur, Dipolmoment und ¹⁴N-Kernquadrupolkopplungskonstante des Acetonitril-N-Oxids aus dem Mikrowellenspektrum / Structure, Dipole Moment and ¹⁴N-Nuclear Quadrupole Coupling Constant of Acetonitrile-N-Oxide from the Microwave Spectrum

Cited by 22 publications

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Structural and spectroscopic characterization of methyl isocyanate, methyl cyanate, methyl fulminate, and acetonitrile N-oxide using highly correlated ab initio methods

Structural and spectroscopic characterization of methyl isocyanate, methyl cyanate, methyl fulminate, and acetonitrile N-oxide using highly correlated ab initio methods

Nitrilimine: von der Charakterisierung in Matrix zu stabilen Verbindungen

Nitrile Imines: From Matrix Characterization to Stable Compounds

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Struktur, Dipolmoment und 14N-Kernquadrupolkopplungskonstante des Acetonitril-N-Oxids aus dem Mikrowellenspektrum / Structure, Dipole Moment and 14N-Nuclear Quadrupole Coupling Constant of Acetonitrile-N-Oxide from the Microwave Spectrum

Cited by 22 publications

References 0 publications

Structural and spectroscopic characterization of methyl isocyanate, methyl cyanate, methyl fulminate, and acetonitrile N-oxide using highly correlated ab initio methods

Structural and spectroscopic characterization of methyl isocyanate, methyl cyanate, methyl fulminate, and acetonitrile N-oxide using highly correlated ab initio methods

Nitrilimine: von der Charakterisierung in Matrix zu stabilen Verbindungen

Nitrile Imines: From Matrix Characterization to Stable Compounds

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Struktur, Dipolmoment und ¹⁴N-Kernquadrupolkopplungskonstante des Acetonitril-N-Oxids aus dem Mikrowellenspektrum / Structure, Dipole Moment and ¹⁴N-Nuclear Quadrupole Coupling Constant of Acetonitrile-N-Oxide from the Microwave Spectrum