ISSN:
1432-2234
Keywords:
Energy partitioning
;
Isomerization
;
Cyanide
;
Methyl isocyanide
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
Notes:
Abstract CNDO/2 calculations together with a partitioning of the energy into various one- and two-centre components have been performed on CH3CN, CH3NC, and a large number of nuclear configurations formed by placing the methyl group at various positions with respect to the fixed CN group. A complete potential energy surface was obtained showing that a minimum in energy occurred for a pyramidal CH3 group placed at approximately 90° to the CN axis. The barrier to the reaction CH3NC→CH3CN is calculated as 32.9 kcal, in reasonable agreement with 38.4 kcal, the experimental value of Rabinovitch. A charge separation equivalent to [CH 3 +0.22 ][CN−0.22] is found for the intermediate compared to [CH 3 +0.08 ][CN−0.08] and [CH 3 +0.12 ][NC−0.22] for the cyanide and isocyanide, respectively.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF00528489
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