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

• Main Author: Kelley, Douglas
• Other Authors: United States. Department of Energy. Office of Energy Research.
• Format: Thesis
• Language: English
• Published: Ames Laboratory 1990
• Subjects: Elements; Chemical Reactions; Transition Element Complexes; Hormone Antagonists; Drugs; Chemical Reaction Yield; Chemical Reaction Kinetics; Complexes; Cobalt Complexes; Thiocyanates; Reaction Kinetics; Chlorides; Transition Element Compounds; Oxygen; Antithyroid Drugs; Kinetics; Refractory Metal Compounds; Photolysis; Organic Sulfur Compounds; Organic Compounds; Halogen Compounds; Alkyl Radicals; Ethyl Radicals; Ruthenium Complexes; Yields 400201* > Chemical & Physicochemical Properties; Bromine Compounds; Chlorine Compounds; Radicals; Halides; Carbonic Acid Derivatives; Nitriles; 37 Inorganic; Organic; Physical And Analytical Chemistry; Photochemical Reactions; Organic Nitrogen Compounds; Nickel Complexes; Iridium Chlorides; Iridium Compounds; Decomposition; Acetonitrile; Nonmetals; Carbonic acid
• Online Access: https://doi.org/10.2172/6454295; https://digital.library.unt.edu/ark:/67531/metadc1212845/

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.