ISSN:
0192-8651
Keywords:
Computational Chemistry and Molecular Modeling
;
Biochemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Computer Science
Notes:
Ab initio calculations of the potential energy surfaces of CH2N2, CHFN2, and CF2N2 at MP4SDTQ/6-31G*//MP2(full)/6-31G* reveal several surprising features. While diazomethane is more stable than diazirine, only the three-membered ring forms of the fluorine-substituted isomers are known experimentally. We find fluorodiazomethane and difluorodiazomethane not to be viable species: They have no barriers toward exothermic dissociation into N2 and CHF or CF2, respectively. In contrast, the three-membered ring isomers, fluorodiazirine and difluorodiazirine, have high barriers toward dissociation despite being high in energy. Diazomethane bends easily; a nonplanar Cs minimum is found at MP2(full)/6-31G* but C2v symmetry is preferred at QCISD/6-31G*. © 1992 by John Wiley & Sons, Inc.
Additional Material:
5 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/jcc.540130905
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