ISSN:
0020-7608
Keywords:
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The reaction pathway of fulminic acid (HCNO) and acetonitrile oxide (CH3CNO) with methanol as a nucleophile (RCNO + CH3OH → RC(OCH3)=NOH) and the formation of H-bonded complex with methanol have been studied using the MNDO method. MNDO-SCF calculations were performed with complete geometry optimization using the Davidon-Fletcher-Powell method. The reaction pathways were studied by varying all the bond lengths, the bond angles and the twist angles, using the distance C3—O2(R) between the carbon of the 1,3-dipoles and the oxygen of the methanol molecule as the reaction coordinate. The reaction is exothermic and proceeds in two steps. The first step is the formation of a five-centered hydrogen-bonded complex (INT) and is the rate-determining step of the reaction. The second step involves the rearrangement of the H-bonded complex to the product, and this step requires a very small amount of activation energy. Thus, there is an intermediate on the reaction pathway, and therefore, the reaction is stepwise. Acetonitrile oxide is less reactive (activation energy 34.59 kcal/mol) relative to fulminic acid (activation energy 28.91 kcal/mol).
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/qua.560300203
