Extended Hückel theory—vi
1966; Elsevier BV; Volume: 22; Issue: 2 Linguagem: Inglês
10.1016/0040-4020(66)80021-2
ISSN1464-5416
Autores Tópico(s)Photochemistry and Electron Transfer Studies
ResumoApproximate calculations are presented for the excited states of diazirine and diazomethane. The long wavelength transition in the former is assigned as allowed, B1 ← A1 π* ← σ; in the latter as forbidden A2 ← A1, σ* ← π. Tentative assignments are made for higher excited states. The change in molecular bonding upon excitation is consistent with the observed primary photochemical processes: dissociation to carbenes and N2 in diazoalkanes, similar dissociation or rearrangement to diazomethanes in the diazirines. The latter isomerization is followed theoretically in some detail, and the role of geometrical changes in the various excited states of diazirine and diazomethane is examined.
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