Structure and reactivity of novel alkylcobalt macrocycles

Journal Article · Wed Sep 05 04:00:00 EDT 1990 · Inorganic Chemistry; (USA)

DOI:https://doi.org/10.1021/ic00343a032· OSTI ID:6113236

Lee, Shaoyung; Espenseon, J H; Bakac, A ^[1]

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1. Ames Lab., IA (USA) Iowa State Univ., Ames (USA)

The organocobalt complexes ((H{sub 2}O)LCoR)(ClO{sub 4}){sub 2} (R = primary alkyl, substituted primary alkyl; L = Me{sub 6}(14)4,11-dieneN{sub 4} (L{sup 1}), C-meso-Me{sub 6}(14)aneN{sub 4}(L{sup 2})) were prepared photochemically from the corresponding alkylcobaltoximes. A modified Fenton reaction also yielded the organocobalt complexes. The complexes were characterized by {sup 1}H NMR and visible spectroscopies and crystal structure determination for (N-rac-(H{sub 2}O)L{sup 1}CoCH{sub 2}Cl)(ClO{sub 4}){sub 2}. The unit cell dimensions are reported. The alkylcobalt complexes (R = C{sub 2}H{sub 5}, n-C{sub 3}H{sub 7}) undergo unimolecular homolysis; the activation enthalpy for this process is 24-26 kcal/mol. The rates of the alkyl group transfer between Cr{sup 2+} and LCoR{sup 2+} in H{sub 2}O show a strong dependence on steric effects of the alkyl group, consistent with an S{sub H}2 mechanism. 46 refs., 3 figs., 8 tabs.

• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 6113236
• Journal Information: Inorganic Chemistry; (USA), Journal Name: Inorganic Chemistry; (USA) Vol. 29:18; 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
400500 -- Photochemistry
CHEMICAL PREPARATION
CHEMISTRY
COBALT COMPLEXES
COMPLEXES
CRYSTAL STRUCTURE
DATA
DIENES
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHOTOCHEMISTRY
POLYENES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES