Redox processes and alkylation reactions of C[sub 60] as studied by pulse radiolysis

Journal Article · Thu Oct 28 00:00:00 EDT 1993 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100145a024· OSTI ID:5652013

Guldi, D M; Hungerbuehler, H; Janata, E; Asmus, K D ^[1]

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1. Hahn-Meitner-Institut, Berlin (Germany)

Redox and alkylation (radical addition) reactions with C[sub 60] have been investigated by means of radiation chemical methods, particularly time-resolved radiolysis measurements. All experiments were conducted in solutions at room temperature. The primary radical products, namely, the C[sub 60][sup [sm bullet][minus]] radical anion, the C[sub 60][sup [sm bullet]+] radical cation and radical adducts (C[sub 60]-R)[sup [sm bullet]], exhibit distinct absorption bands in the IR at 1080, 980 (corroborating earlier low-temperature matrix and photochemical experiments), and around 900 nm, respectively. Reductions, to yield the C[sub 60][sup [sm bullet][minus]] radical anion (and at longer steady-state irradiations also more highly reduced states), could be achieved by solvated electrons and (CH[sub 3])[sub 2]C(OH)[sup [sm bullet]] radicals in 2-propanol solutions and toluene/acetone/2-propanol mixtures with rate constants of [ge]10[sup 10] and 8.5 x 10[sub 8] M[sup [minus]1] s[sup [minus]1], respectively. The reaction of a water-soluble C[sub 60]-[gamma]-cyclodextrin complex (C[sub 60]/[gamma]-CD) with [alpha]-hydroxyalkyl radicals also involves electron transfer, as indicated by the dependence of the rate constants on the redox potential of the reducing radicals: 2.7 [times] 10[sup 8] M[sup [minus]1] s[sup [minus]1] for (CH[sub 3])[sub 2]C(OH)[sup [sm bullet]], 1.4 [times] 10[sup 8] M[sup [minus]1] s[sup [minus]1] for CH[sub 3]CH(OH)[sup [sm bullet]], and 0.5 [times] 10[sup 8] M[sup [minus]1] s[sup [minus]1] for [sup [sm bullet]]CH[sub 2](OH). 44 refs., 9 figs., 2 tabs.

• OSTI ID: 5652013
• Journal Information: Journal of Physical Chemistry; (United States), Vol. 97:43; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE
FULLERENES
ALKYLATION
RADIOLYSIS
REDOX REACTIONS
CHEMICAL REACTION KINETICS
COMPLEXES
INFRARED SPECTRA
POLYMERIZATION
PULSED IRRADIATION
RADICALS
CARBON
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
DECOMPOSITION
ELEMENTS
IRRADIATION
KINETICS
NONMETALS
RADIATION EFFECTS
REACTION KINETICS
SPECTRA
400201* - Chemical & Physicochemical Properties
360605 - Materials- Radiation Effects