Electron Transfer. 134. Reduction of Bound Ruthenium(III) by Indium(I)<sup>1</sup>
作者:Swapan K. Chandra、Edwin S. Gould
DOI:10.1021/ic961393z
日期:1997.7.1
of the metal centers involved in the net transfer. The rate for the reduction of (NH(3))(6)Ru(3+), considered in the framework of the Marcus model, leads to an estimated rate constant of 10(-9) M(-1) s(-1) for electron self-exchange in the system In(2+/+). This value lies well below the range characteristic of the most usual aqua-substituted cationic couples, suggesting a more severe H(2)O-metal bond
of the couples NiLi2+/NiLi+, L = tetraaza-14-membered-macrocyclic ligands, and on the properties of the monovalentnickel complexes in aqueoussolutions are reported for 14 complexes. The spectra and lifetimes of the NiLi+ complexes are reported. The self-exchange rates for the couples NiLi2+/NiLi+ were determined. Two of the ligands were synthesized for the first time for this study. Cyclic voltammetry
对于14种络合物,报道了N-烷基化对NiL i 2+ / NiL i +,L =四氮杂14元大环配体对的氧化还原电势的影响,以及对水溶液中一价镍络合物性质的影响。 。报告了NiL i +配合物的光谱和寿命。NiL i 2+ / NiL i +夫妇的自交换率被确定。本研究首次合成了两个配体。使用循环伏安法和脉冲放射分解法。结果表明:(i)N-烷基化总是将氧化还原电势转移到阴极电势较低的地方;这种作用在很大程度上是由于配体的N-烷基化引起的配合物溶剂化能的降低。(ii)。一价络合物的寿命与NiL i 2+ / NiL i +对的氧化还原电位没有线性关系。(iii)NiL i +配合物以几种异构形式存在;异构化的速率取决于配体的结构。(iv)NiL i +的不同异构体当复合NiL i 2+被不同的试剂还原时,可能会形成该化合物。因此,脉冲辐照形成的NiL i +络合物可能具有与电化学形成的性质不同的性质。
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
Charge-transfer perturbations of the electronic contributions to bimolecular reactions. Nonadiabatic effects observed in energy-transfer and electron-transfer reactions
作者:John F. Endicott、T. Ramasami、Dennis C. Gaswick、R. Tamilarasan、Mary Jane Heeg、George R. Brubaker、Stephen C. Pyke
DOI:10.1021/ja00354a020
日期:1983.8
Les vitesses de transfert d'energie intermoleculaire entre ( 2 E) Cr (polypyridyl) 3 3+ et les complexes de Co(III) et les vitesses de transfert d'electron intermoleculaire entre Co (polypyr) 3 3+ et CO(sup) 2+ sont sensibles aux faibles perturbations de transfert de charge pour certaines combinaisons de reactifs
Les vitesses de transfert d'energie interleculaire entre (2 E) Cr (polypyridyl) 3 3+ et les complexes de Co(III) et les vitesses de transfert d'electron interleculaire entre Co (polypyr) 3 3+ et CO(sup) 2+ sont sensibles aux faibles perturbations de transfert de charge pour surees combinaisons de reactifs
The Reductions of Azido–, Thiocyanato–, and Isothiocyanato–pentacyanocobaltate(III) Anions by Titanium(III) in Aqueous Acidic Solution
作者:Olayinka Oyetunji、Olusegun Olubuyide、J. Folorunso Ojo
DOI:10.1246/bcsj.63.601
日期:1990.2
The reductions of azido–, thiocyanato–, and isothiocyanato–pentacyanocobaltate(III) anions by aquatitanium(III) have been studied in aqueoussolution with I=1.0 mol dm−3 (LiCl) T=25°C. The reactions are found to have inverse acid dependence of the form: kobsd=kK⁄(K+[H+]).The estimated values of k and K are 1.47 dm3mol−1 s−1 and 1.0×10−2 mol dm−3 for the azido complex and 4.85 dm3mol−1s−1 and 6.0×10−3