- Spectroscopic and Kinetic Characterization of Diphenyldiazomethane Radical Anion
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Diphenyldiazomethane radical anion (Ph2CN2.-) has been generated by radiolytic reduction of diphenyldiazomethane (Ph2CN2) in both protic and aprotic solvents.The absolute kinetics of formation and reactivity of Ph2CN2.- were obtained by monitoring its transient absorption (λmax = 355-370 nm) following nanosecond pulse radiolysis.In isopropylalcohol, reaction of the solvated electron with Ph2CN2 forms Ph2CN2.- (λmax =355 nm), which subsequently protonates to form Ph2C.N2H), as detected by a sharp absorption band at 330 nm.In aprotic solvents and in the ab sence of added quenchers, Ph2CN2.- decays primarily by pseudo-first-order reaction with Ph2CN2.With added weak organic acids protonation of Ph2CN2.- also occurs.Ph2CN2.- reacts with molecular oxygen with a near diffusion-controlled rate; however, it demonstrates no reactivity toward hydrogen atom donors, and no evidence of thermal loss of N2 to produce diphenylcarbene radical anion was observed.
- Chateauneuf, John. E.
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