title: Photolysis of dimethylcarbamoyl azide in an argon matrix: spectroscopic identification of dimethylamino isocyanate and 1,1-dimethyldiazene.
abstract: The UV photolysis of dimethylcarbamoyl azide has been investigated in an argon matrix at cryogenic temperatures. The products of the photolysis were identified by infrared spectroscopy supported by quantum-chemical calculations. Sequential formation of dimethylamino isocyanate (Me2N-NCO), 1,1-dimethyldiazene (Me2N═N), and ethane was established. Therefore, the major decomposition channel is identified as Me2NC(O)N3 → Me2N-NCO → Me2N═N → Me-Me, via consecutive N2, CO, and N2 eliminations. Ground-state geometries, vibrational frequencies, IR intensities, and UV excitation energies of the transient dimethylamino isocyanate and 1,1-dimethyldiazene have been computed using the B3LYP and SAC-CI methods and the aug-cc-pVTZ basis set.
authors.affiliation: Institute of Chemistry, Eötvös Loránd University , P.O. Box 32, H-1518 Budapest 112, Hungary.
authors.forename: Tibor
authors.initials: T
authors.lastname: Pasinszki
authors.forename: Melinda
authors.initials: M
authors.lastname: Krebsz
authors.forename: György
authors.initials: G
authors.lastname: Tarczay
authors.forename: Curt
authors.initials: C
authors.lastname: Wentrup