Electron transfer reactions of tris(polypyridine)cobalt(III) complexes, [Co(N-N)(3)](3+), with verdazyl radicals in acetonitrile solution

Keeney L; Hynes MJ

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Electron transfer reactions of tris(polypyridine)cobalt(III) complexes, [Co(N-N)(3)](3+), with verdazyl radicals in acetonitrile solution

机译：三（聚吡啶）钴（III）配合物[Co（N-N）（3）]（3+）与维达唑基在乙腈溶液中的电子转移反应

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The kinetics and mechanisms of the reactions of 3-(4-X)-phenyl-1,5-diphenyl-verdazyl radicals where X = Cl, H, CH3 and CH3O with [Co(N - N)(3)](3+), N - N = 2,2'-bipyridyl (bpy), 1,10-phenanthroline (phen) and 4,7-dimethyl-1,10- phenanthroline (4,7-Me(2)phen), have been investigated in acetonitrile at 25degreesC and ionic strength 0.05 mol dm(-3) ((C4H9)-C-n)(4)NPF6 using stopped flow spectrophotometry. In all cases, transfer of one electron from the radical takes place resulting in the production of a Co(II) species and a verdazylium cation. The electron transfer occurs by an outer-sphere mechanism and the reactions appear to be consistent with Marcus theory. The self-exchange rate constants for the verdazyl-verdazylium cation have been estimated and are of the order of 3.4(+/- 1.9) x 10(7) dm(3) mol(-1) s(-1). This rate constant is consistent with the fact that the reactions of [Ru(bpy)(3)](3+) with verdazyl radicals are too rapid to be investigated by stopped flow spectrophotometry.

机译：X = Cl，H，CH3和CH3O的3-（4-X）-苯基-1,5-二苯基-哒唑基与[Co（N-N）（3）]（3）的反应动力学和机理+），N-N = 2,2'-联吡啶（bpy），1,10-菲咯啉（phen）和4,7-二甲基-1,10-菲咯啉（4,7-Me（2）phen）具有用乙炔在25°C和离子强度为0.05 mol dm（-3）（（（C4H9）-Cn）（4）NPF6的情况下使用停止流光度法进行了研究。在所有情况下，都会发生一个电子从自由基的转移，导致产生Co（II）物种和维达兹阳离子。电子转移是通过外层机制发生的，并且反应似乎与马库斯理论一致。估算了verdazyl-verdazylium阳离子的自交换速率常数，其常数为3.4（+/- 1.9）x 10（7）dm（3）mol（-1）s（-1）。该速率常数与[Ru（bpy）（3）]（3+）与Verdazyl自由基的反应太快而无法通过停止流式光度法研究的事实是一致的。

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《Dalton transactions: An international journal of inorganic chemistry》 |2005年第1期|共6页
作者
Keeney L; Hynes MJ;
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正文语种 eng
中图分类无机化学;
关键词
CHARGE-TRANSFER PERTURBATIONS; SUBSTITUTED PARA-PHENYLENEDIAMINES; SELF-EXCHANGE KINETICS; AQUEOUS-SOLUTION; COBALT(III) COMPLEXES; RATE CONSTANTS; MARCUS THEORY; POLYPYRIDINE COMPLEXES; ACTIVATION PARAMETERS; BIMOLECULAR REACTIONS;

机译：电荷转移扰动;取代的对苯二胺;自交换动力学;水溶液;钴（III）络合物;速率常数;马库斯理论;聚吡啶络合物;活化参数;双分子反应;

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1. Electron transfer reactions of tris(polypyridine)cobalt(III) complexes, [Co(N-N)(3)](3+), with verdazyl radicals in acetonitrile solution [J] . Keeney L, Hynes MJ Dalton transactions: An international journal of inorganic chemistry . 2005,第1期

机译：三（聚吡啶）钴（III）配合物[Co（N-N）（3）]（3+）与维达唑基在乙腈溶液中的电子转移反应
2. Electron transfer reactions of bis(1,4,7-trithiccyclononane) palladium(III/II), -platinum(III/II), and –gold(III/II) complexes in aqueous solution and in acetonitrile [J] . M.Matsumoto, M.Itoh Canadian Journal of Chemistry . 1999,第10期

机译：双（1,4,7-三硫环壬烷）钯（III / II），-铂（III / II）和-金（III / II）配合物在水溶液和乙腈中的电子转移反应
3. Electron transfer reaction of Tris(1,10-phenanthroline) cobalt(III) complex [Co(phen)3]3+ and thiosulphate ion (S2O32?) in an aqueous acidic medium [J] . C R. Osunkwo, I U. Nkole, A D. Onu, International Journal of Advanced Chemistry . 2018,第1期

机译：三（1,10-菲咯啉）钴（III）配合物[Co（phen）3] 3+与硫代硫酸根离子（S2O32？）的电子转移反应
4. Highly Enantioselective Diels-Alder Reactions of Danishefsky's-type Dienes with Electron-Deficient Alkenes Catalyzed by Yb(III)-BINAMIDE Complexes [C] . Daisuke Shirasaki, Yukinori Sudo, Shinji Harada Symposium on Organometallic Chemistry . 2007

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机译：一，吩噻嗪与三（二亚胺）钌（II）配合物之间的基态缔合：在高效光诱导电荷分离中的作用。二。钴配合物的配体修饰，以提高染料敏化太阳能电池中电子转移介体的效率
6. Verdazyls as Possible Building Blocks for Multifunctional Molecular Materials: A Case Study on 15-Diphenyl-3-(p-iodophenyl)-verdazyl Focusing on Magnetism Electron Transfer and the Applicability of the Sonogashira-Hagihara Reaction [O] . Hannah Jobelius, Norbert Wagner, Gregor Schnakenburg, 2018

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8. Kinetic Study of the Oxygen-Transfer Reactions from the Oxo Diperoxo Complexes of Molybdenum(VI) and Tungsten(VI) to (Thiolato)- and (Sulfenato)cobalt(III) Complexes [R] . Ghiron, A. F., Thompson, R. C. 1988

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Electron transfer reactions of tris(polypyridine)cobalt(III) complexes, [Co(N-N)(3)](3+), with verdazyl radicals in acetonitrile solution

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