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

机译：烷基与氧以及与Co（III），Ru（III）和Ni（III）的络合物反应的动力学和机理。

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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.

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作者
Kelley, D.;
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年度 1990
页码 1-179
总页数 179
原文格式 PDF
正文语种 eng
中图分类工业技术;
关键词
Alkyl Radicals; Cobalt Complexes; Ethyl Radicals; Nickel Complexes; Ruthenium Complexes; Acetonitrile; Bromine Compounds; Chemical Reaction Kinetics; Chemical Reaction Yield; Chemical Reactions; Chlorine Compounds; Iridium Chlorides; Oxygen; Photolysis; Thiocyanates; EDB/400201; Theses;

机译：烷基自由基;钴配合物;乙基自由基;镍配合物;钌配合物;乙腈;溴化合物;化学反应动力学;化学反应产率;化学反应;氯化合物;氯化铱;氧;光解;硫氰酸盐; EDB / 400201;论文;以及它们的组合。;

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7. Kinetics and mechanisms of the reactions of alkyl radicals with oxygen and with complexes of Co(III), Ru(III), and Ni(III) [O] . D. Kelley 1990

机译：烷基与氧气反应的动力学和机制及CO（III），Ru（III）和Ni（III）的复合物
8. Kinetics and mechanisms of the reactions of alkyl radicals with oxygen and with complexes of Co(III), Ru(III), and Ni(III) [R] . Kelley, D. 1990

机译：烷基与氧以及与Co（III），Ru（III）和Ni（III）配合物反应的动力学和机理

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

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