ISSN:
0192-8651
Keywords:
Computational Chemistry and Molecular Modeling
;
Biochemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Computer Science
Notes:
Vinyloxyboranes, CH2=CH—;O—;BR2, are shown by ab initio molecular orbital theory to be more stable than the isomeric β-aldoboranes, R2B—CH2—CH=O, by ca. 19 kcal/mol. The MP2/6-31G*/6-31G* + ZPE barrier for the [1,3] boron shift is only 10.9 kcal/mol (R = Me) relative to the aldoborane. Other C2H5BO isomers (β-ketoboranes, boraepoxides and organoboron oxides), which are related to the proposed stages in the carbonylation reaction of boranes, are shown to be plausible intermediates. However, some of the computed barriers for methyl group migrations are unrealistically large, up to ca. 63 kcal/mol.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/jcc.540130405
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