ISSN:
0192-8651
Keywords:
cyanate
;
isocyanate
;
ambident
;
ion pair
;
SN2 reaction
;
Chemistry
;
Theoretical, Physical and Computational Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Computer Science
Notes:
The structure of lithium and sodium cyanates and isocyanates and their related ion pair SN2 reactions were investigated using molecular quantum mechanics at the Hartree-Fock (HF)/6-31G**//HF/6-31G** level. Extensive further calculations of some of the lithium systems at higher levels gave no significant changes in relative properties. The isocyanate ion pairs are the most stable monomeric forms. The lowest energy dimers are planar eight-membered rings. For the ionic SN2 reaction of cyanate ion and methyl fluoride and chloride, methyl isocyanate is the predicted major product. The monomer ion pair inversion mechanism is predicted to preferentially form methyl cyanate but the calculations also indicate that reaction with dimeric ion pairs have no clear preference for forming methyl cyanate or isocyanate. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 1325-1336, 1998
Additional Material:
9 Ill.
Type of Medium:
Electronic Resource
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