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

Journal Article · Wed Nov 29 00:00:00 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), Vol. 28:24; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

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