Electron-transfer reactions between C[sub 60] and radical ions of metalloporphyrins and arenes

Journal Article · Thu Apr 28 04:00:00 EDT 1994 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100068a022· OSTI ID:7165759

Guldi, D M ^[1]; Neta, P ^[2]; Asmus, K D ^[3]

---

1. National Inst. of Standards and Technology, Gaithersburg, MD (United States) Hahn-Meitner-Inst., Berlin (Germany)
2. National Inst. of Standards and Technology, Gaithersburg, MD (United States)
3. Hahn-Meitner-Inst., Berlin (Germany)

Electron-transfer reactions with C[sub 60] leading to the singly reduced and oxidized radical ions, C[sub 60][sup [sm bullet][minus]] c[sub 60][sup [sm bullet]+], have been studied by pulse radiolysis. [pi]-Radical anions of several metalloporphyrins (tetraphenyl- and tetrapyridylporphyrins) reduced C[sub 60] with rate constants of (1-3) x 10[sup 9] L mol[sup [minus]1] s[sup [minus]1], whereas metalloporphyrins which are reduced at the metal center (Ni[sup I], Cu[sup I], Cr[sup II]) reacted with C[sub 60] somewhat more slowly, with rate constants of (0.7-2.3) x 10[sup 8] L mol[sup [minus]1] s[sup [minus]1]. Sb[sup V]OEP[sup [sm bullet][minus]] (octaethylporphyrin) did not reduce C[sub 60] (k [le] 10[sup 7] L mol[sup [minus]1] s[sup [minus]1]) and Sn[sup IV](Ph)[sub 3](Py)P[sup [sm bullet][minus]] reacted in an equilibrium process (K = 14). Electron transfer from C[sub 60] to several aromatic radical cations (derived from naphthalene, biphenyl, m-terphenyl, and trans-stilbene) also took place rapidly (k = (2.5-7.9) x 10[sup 9] L mol[sup [minus]1] s[sup [minus]1]) to produce C[sub 60][sup [sm bullet]+]; the radical cations of anthracene and chrysene, on the other hand, did not exhibit any significant reactivity toward C[sub 60]. 24 refs., 6 figs., 2 tabs.

• OSTI ID: 7165759
• Journal Information: Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 98:17; ISSN JPCHAX; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
99 GENERAL AND MISCELLANEOUS
990200 -- Mathematics & Computers
AROMATICS
CARBON
CARBOXYLIC ACIDS
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPILED DATA
DATA
DECOMPOSITION
ELECTRON TRANSFER
ELEMENTS
FULLERENES
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INFORMATION
KINETICS
MATHEMATICAL MODELS
NONMETALS
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PORPHYRINS
RADIATION EFFECTS
RADICALS
RADIOLYSIS
REACTION KINETICS
REDUCTION