Reactions of cobalt(II) macrocycles with alkyl and alkylperoxy radicals

Journal Article · Wed Nov 29 04:00:00 EST 1989 · Inorganic Chemistry; (USA)

DOI:https://doi.org/10.1021/ic00323a007· OSTI ID:6971779

Bakac, A; Espenson, J H ^[1]

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1. Ames Lab., IA (USA)

The cobalt-carbon bond formation in the reactions of cobalt(II) macrocyles, LCo{sup II} (L = C-meso-Me{sub 6}(14)aneN{sub 4}, Me{sub 6}(14)-4,11-dieneN{sub 4}, corrin, tim), with primary alkyl and substituted primary alkyl radicals takes place with rate constants in the range 10{sup 7}-10{sup 9} M{sup {minus}1} s{sup {minus}1}. The kinetics are influenced by the nature of the macrocycle to a much greater extent than by the nature of the radicals, such that all the rate constants, k{sub Co}, for a given cobalt complex fall within a factor of {approx} 1. For example, the values of 10{sup {minus}8}k{sub Co}/M{sup {minus}1} s{sup {minus}1} for B{sub 12r} are 4.2 (R = CH{sub 3}), 5.1 (C{sub 2}H{sub 5}), 5.1 (CH{sub 3}OCH{sub 2}), 5.8 (ClCH{sub 2}), 6.1 (C{sub 3}H{sub 7}), and 9.1 (BrCH{sub 2}). The alkylperoxy radicals RO{sub 2}{sup {sm bullet}} (R = CH{sub 3}, C{sub 2}H{sub 5}, BrCH{sub 2}) react with Co(tim)(H{sub 2}O){sub 2}{sup 2+} with a rate constant k = 1.4 {times} 10{sup 8} M{sup {minus}1} s{sup {minus}1}. 31 refs., 2 figs., 1 tab.

• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 6971779
• Journal Information: Inorganic Chemistry; (USA), Journal Name: Inorganic Chemistry; (USA) Vol. 28:24; ISSN 0020-1669; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKYL RADICALS
CHEMICAL BONDS
CHEMICAL REACTIONS
COBALT COMPLEXES
COMPLEXES
DATA
EXPERIMENTAL DATA
HETEROCYCLIC COMPOUNDS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PEROXY RADICALS
RADICALS
TRANSITION ELEMENT COMPLEXES