Reactions of alkyl and fluoroalkyl radicals with nickel, iron, and manganese porphyrins
- National Institute of Standards and Technology, Gaithersburg, MD (United States); and others
The reactions of alkyl (CH{sub 3}, C{sub 2}H{sub 5}, n-C{sub 4}H{sub 9}, CH{sub 2}CO{sub 2}{sup {minus}}, CH(CO{sub 2}{sup {minus}}){sub 2}, CH{sub 2}CN) and fluoroalkyl (CF{sub 3}, CF{sub 2}Cl) radicals with nickel, iron, and manganese porphyrins (P) have been studied by radiolytic techniques in various solvents. All the radicals (R) react with Fe{sup II}P to form R-Fe{sup III}P with a stable Fe-C bond. These products are oxidized by O{sub 2} to Fe{sup III}P. Although Ni{sup I}P and Ni{sup II}P also react rapidly with the radicals to form Ni-C bonds, only the reactions of fluoroalkyl radicals with Ni{sup I}P yield stable products. Reactions of alkyl radicals with Ni{sup II}P are reversible and the short-lived R-Ni{sup III} products (t{sub {1/2}}{approximately} milliseconds) disappear through radical reactions, with recovery of Ni{sup II}P. Alkyl radicals react rapidly with Mn{sup II}P, probably via addition to the metal, but the adduct gives Mn{sup III}P immediately. {sup {sm_bullet}}CF{sub 3} radicals also react with Mn{sup III}P by addition to C{double_bond}C bonds. 35 refs., 5 figs.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 563422
- Journal Information:
- Journal of Physical Chemistry, Journal Name: Journal of Physical Chemistry Journal Issue: 23 Vol. 96; ISSN JPCHAX; ISSN 0022-3654
- Country of Publication:
- United States
- Language:
- English
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