A pulse radiolysis study of the rate of ligand dissociation from mixed ligand cobalt(ii) complexes
作者:Alison M. Funston、W. David McFadyen、Peter A. Tregloan
DOI:10.1039/b107392n
日期:2002.4.26
determined. The mechanism of reduction of the cobalt(III) centre by e−aq has been found to vary depending upon the nature of the ligands present in the complex. When an aromatic ligand is present the formation of a coordinated ligand radical is observed. This decays via intramolecular electron transfer to produce the cobalt(II) complex. The rate constants for the intramolecular electron transfer processes
A Definitive Example of a Geometric “Entatic State” Effect: Electron-Transfer Kinetics for a Copper(II/I) Complex Involving A Quinquedentate Macrocyclic Trithiaether−Bipyridine Ligand
作者:Gezahegn Chaka、Jason L. Sonnenberg、H. Bernhard Schlegel、Mary Jane Heeg、Gregory Jaeger、Timothy J. Nelson、L. A. Ochrymowycz、D. B. Rorabacher
DOI:10.1021/ja068960u
日期:2007.4.1
([15]aneS3bpy = L), containing two pyridyl nitrogens and three thiaether sulfurs as donor atoms, has been synthesized and complexed with copper. The CuII/IL redox potential, the stabilities of the oxidized and reduced complex, and the oxidation and reduction electron-transfer kinetics of the complex reacting with a series of six counter reagents have been studied in acetonitrile at 25 degrees C, mu = 0.10 M (NaClO4)
Electron transfer reactions of tris(polypyridine)cobalt(<scp>iii</scp>) complexes, [Co(N–N)<sub>3</sub>]<sup>3+</sup>, with verdazyl radicals in acetonitrile solution
作者:Lynette Keeney、Michael J. Hynes
DOI:10.1039/b412569j
日期:——
7-dimethyl-1,10-phenanthroline (4,7-Me2phen), have been investigated in acetonitrile at 25 degrees C and ionic strength 0.05 mol dm(-3)(nC4H9)4NPF6 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 electrontransfer occurs by an outer-sphere mechanism and the reactions appear to
Comparative study of donor atom effects on the thermodynamic and electron-transfer kinetic properties of copper(<scp>ii</scp>/<scp>i</scp>) complexes with sexadentate macrocyclic ligands. [Cu<sup>II/I</sup>([18]aneS<sub>4</sub>N<sub>2</sub>)] and [Cu<sup>II/I</sup>([18]aneS<sub>4</sub>O<sub>2</sub>)]
作者:Gezahegn Chaka、Ashoka Kandegedara、Mary Jane Heeg、D. B. Rorabacher
DOI:10.1039/b612252c
日期:——
Studies have been conducted on the copper complexes formed with two sexadentate macrocyclic ligands containing four thioether sulfur donor atoms plus either two nitrogen or two oxygen donor atoms on opposing sides of the ring. The resulting two ligands, L, designated as [18]aneS4N2 and [18]aneS4O2, respectively, represent homologues of the previously studied Cu(II/I) system with a macrocycle having
已经对由两个六齿大环形成的铜配合物进行了研究。 配体 包含四个硫醚硫供体原子加上两个 氮或在环相对两侧的两个氧供体原子。结果两个配体分别表示为[18] aneS 4 N 2和[18] aneS 4 O 2的L代表先前研究的Cu(II / I)系统的同系物,大循环具有六个硫供体原子,[18] aneS 6。在这项工作中已经确定了[Cu II([18] aneS 4 O 2)](ClO 4)2和[Cu I([18] aneS 4 O 2)] ClO 4的晶体结构。比较所有三个系统的结构,发现氧化的络合物是六配位,两个配位键在断裂时发生断裂。减少。但是,伴随的几何变化电子转移这三个系统似乎有所不同。两种杂大环配合物的稳定性常数和电化学性质已在乙腈同时研究了Cu II / IL的电子转移动力学溶剂每个系统使用六种不同的抗衡试剂。然后,使用马库斯(Marcus)交叉关系计算了电子自交换速率常数。将结果与其他Cu
Redox reactions of [VO(salen)]+/0 couple in acetonitrile: Volume analyses in relation to large chiral recognitions observed for electron self-exchange reactions of [VO(Schiff-Base)]+/0
作者:Yasuhide Sasajima、Motoharu Shimizu、Norie Kuroyanagi、Nobuyuki Kishikawa、Kyoko Noda、Sumitaka Itoh、Hideo D. Takagi、Masahiko Inamo
DOI:10.1016/j.ica.2005.10.028
日期:2006.1
measurements were carried out for the outer-sphere electron transfer reactions involving [VO(Schiff-Base)]+/0 couples. Electron self-exchangerate constant for [VO(3-MeOsal-(RR)-chxn)]+/0 couple was determined as kex = (5.2 ± 0.8) × 106 kg mol−1s−1 at 25 °C. It was found that added water in acetonitrile solvent retarded the electron transfer reactionsbetween [VO(salen)]+ and [Co(o-phen)3]2+: the six-coordinate