engleski

Photoelimination of Nitrogen from Diazoalkanes: Involvement of Higher Excited Singlet States in the Carbene Formation

Although diazoalkanes are important carbene precursors in organic synthesis, a comprehensive mechanism of photochemi-cal formation of carbenes from diazoalkanes has not been proposed. Synergy of experiments and computations demon-strates the involvement of higher excited singlet states in the photochemistry of diazoalkanes. In all investigated diazo-alkanes, excitation to S1 results in nonreactive internal conversion to S0. On the contrary, excitation to higher-lying singlet states (Sn, n > 1), drives the reaction toward a different segment of the S1/S0 conical intersection seam and results in nitrogen elimination and formation of carbenes.

diazoalkanes ; carbenes ; anti-kasha photochemistry

nije evidentirano