Density functional calculations
Wiley InterScience Backfile Collection 1832-2000
Chemistry and Pharmacology
The complex photochemistry of matrix-isolated dihaloformoximes 8a, 8b, and 8c, which are transformed upon irradiation into the new hydrogen-bonded complexes HalCN…HOHal 10a-c′, identified by their IR spectra, has been unveiled. An earlier assignment of the experimental IR absorptions to isofulminic acid HONC (4) must be withdrawn. A competitive reaction to the formation of complexes 10a-c′ produces the hydrogen-bonded complexes HalNCO/HHal 12a-c′, which can be regarded as intermediates on the photochemical pathway to the final product isocyanic acid HNCO (1), and are tentatively identified by their IR absorptions. Our findings are supported by deuteration experiments and theoretical calculations using the density functional method BLYP/6-311G*.
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