Kinetics and mechanisms of the reactions of alkyl radicals with oxygen and with complexes of Co(III), Ru(III), and Ni(III)

Technical Report · Mon Oct 08 00:00:00 EDT 1990

DOI:https://doi.org/10.2172/6454295· OSTI ID:6454295

Kelley, D

The kinetics of the reactions of C{sub 2}H{sub 5} radical with Co(NH{sub 3}){sub 5}X{sup 2+}, Ru(NH{sub 3}){sub 5}X{sup 2+}, and Co(dmgH){sub 2} (X) (Y) (X = Br, Cl, N{sub 3}, SCN; Y = H{sub 2}O, CH{sub 3}CN) complexes were studied using laser flash photolysis of ethylcobalt complexes. The kinetics were obtained by the kinetic probe method. Some relative rate constants were also determined by a competition method based on ethyl halide product ratios. The kinetics of colligation reactions of a series of alkyl radicals with {beta}-Ni(cyclam){sup 2+} were studied using flaser flash photolysis of alkylcobalt complexes. Again, the kinetics were obtained by employing the kinetic probe competition method. The kinetics of the unimolecular homolysis of a series of RNi(cyclam)H{sub 2}O{sup 2+} were studied. Activation parameters were obtained for the unimolecular homolysis of C{sub 2}H{sub 5}Ni(cyclam)H{sub 2}O{sup 2+}. Kinetic and thermodynamic data obtained from these reactions were compared with those for the {sigma}-bonded organometallic complexes. The kinetics of the unimolecular homolysis of a series of RNi(cyclam)H{sub 2}O{sup 2+} complexes were studied by monitoring the formation of the oxygen insertion product RO{sub 2}Ni(cyclam)H{sub 2}O{sup 2+}. The higher rate constants for the reactions of alkyl radicals with oxygen in solution, as compared with those measured in the gas phase, were discussed. 30 refs.

• Research Organization: Ames Lab., Ames, IA (United States)
• Sponsoring Organization: DOE/ER
• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 6454295
• Report Number(s): IS-T-1492; ON: DE91000998; TRN: 90-034749
• Resource Relation: Other Information: Thesis (Ph.D.)
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ALKYL RADICALS
CHEMICAL REACTIONS
COBALT COMPLEXES
ETHYL RADICALS
NICKEL COMPLEXES
RUTHENIUM COMPLEXES
ACETONITRILE
BROMINE COMPOUNDS
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHLORINE COMPOUNDS
IRIDIUM CHLORIDES
OXYGEN
PHOTOLYSIS
THIOCYANATES
ANTITHYROID DRUGS
CARBONIC ACID DERIVATIVES
CHLORIDES
COMPLEXES
DECOMPOSITION
DRUGS
ELEMENTS
HALIDES
HALOGEN COMPOUNDS
HORMONE ANTAGONISTS
IRIDIUM COMPOUNDS
KINETICS
NITRILES
NONMETALS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PHOTOCHEMICAL REACTIONS
RADICALS
REACTION KINETICS
REFRACTORY METAL COMPOUNDS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
YIELDS
400201* - Chemical & Physicochemical Properties