Spectroscopic and kinetic characterization of diphenyldiazomethane radical anion

Journal Article · Thu Sep 06 04:00:00 EDT 1990 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100381a041· OSTI ID:5347736

Chateauneuf, J E ^[1]

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1. Univ. of Notre Dame, IN (USA)

Diphenyldiazomethane radical anion (Ph{sub 2}CN{sub 2}{sup {sm bullet}{minus}}) has been generated by radiolytic reduction of diphenyldiazomethane (Ph{sub 2}CN{sub 2}) in both protic and aprotic solvents. The absolute kinetics of formation and reactivity of Ph{sub 2}CN{sub 2}{sup {sm bullet}{minus}} were obtained by monitoring its transient absorption following nanosecond pulse radiolysis. In isopropyl alcohol, reaction of the solvated electron with Ph{sub 2}CN{sub 2} forms Ph{sub 2}CN{sub 2}{sup {sm bullet}{minus}} ({lambda}{sub max} = 355 nm), which subsequently protonates to form Ph{sub 2}CN{sub 2}H, as detected by a sharp absorption band at 330 nm. In aprotic solvents and in the absence of added quenchers, Ph{sub 2}CN{sub 2}{sup {sm bullet}{minus}} decays primarily by pseudo-first-order reaction with Ph{sub 2}CN{sub 2}. With added weak organic acids protonation of Ph{sub 2}CN{sub 2}{sup {sm bullet}{minus}} also occurs. Ph{sub 2}CN{sub 2}{sup {sm bullet}{minus}} 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 N{sub 2} to produce diphenylcarbene radical anion was observed.

• OSTI ID: 5347736
• Journal Information: Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 94:18; ISSN 0022-3654; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400600 -- Radiation Chemistry
ABSORPTION SPECTROSCOPY
ACTIVATION ENERGY
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
DECOMPOSITION
DIAZO COMPOUNDS
ELECTRONS
ELEMENTARY PARTICLES
ENERGY
FERMIONS
KINETICS
LEPTONS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
RADIATION EFFECTS
RADICALS
RADIOLYSIS
SOLVATED ELECTRONS
SPECTROSCOPY