Kinetics and mechanisms of the electron transfer reactions of oxo-centred carboxylate bridged complexes, [Fe<sub>3</sub>(µ<sub>3</sub>-O)(O<sub>2</sub>CR)<sub>6</sub>L<sub>3</sub>]ClO<sub>4</sub>, with verdazyl radicals in acetonitrile solution
作者:Lynette Keeney、Michael J. Hynes
DOI:10.1039/b418809h
日期:——
L. The kinetics of the electron transfer reaction observed when acetonitrile solutions of the complexes were reacted with a range of verdazyl radicals were monitored using stopped-flow spectrophotometry. Under the experimental conditions, the reactions were quite rapid and were monitored under second-order conditions. Marcus linear free energy plots indicated that the outer-sphere electron transfer
范围为通式[Fe 3(µ 3 -O)(O 2 CR)6 L 3 ] ClO 4 (R = CH 2 CN,CH 2 F,CH 2 Cl的以氧为中心的,羧酸根桥联的三铁配合物,CH 2 Br,p -NO 2 C 6 H 4; L =吡啶, 3-甲基吡啶, 4-甲基吡啶, 3,5-二甲基吡啶, 3-氰基吡啶 和 3-氟吡啶)已准备好并进行了特征化。R和L的选择是由这样的要求决定的,即配合物与凡达唑基反应时,该配合物会发生单电子还原。除L =的复数以外的所有复数吡啶R = CH 2 CN,CH 2 Cl和p -NO 2 C 6 H 4尚未见报道。这些化合物的氧化还原行为已使用循环伏安法 在 乙腈通常,所有络合物均表现出可逆的单电子还原。在过量L的存在下,电化学行为得到改善。乙腈 使配合物溶液与一定范围的Verdazyl自由基反应,并使用停止流进行监测 分光光度法。在实验条件下,反应相当快,并且在
Redox Reactions of<i>cis</i>-Dialkylcobalt(III) Complexes with Benzyl and Allyl Bromides, Induced by Thermal Cleavage of the Cobalt–Carbon Bond
作者:Kunio Ishikawa、Shunichi Fukuzumi、Toshio Tanaka
DOI:10.1246/bcsj.60.563
日期:1987.2
of the thermal cleavage of the cobalt–carbon bond of cis-[R2Co(bpy)2]+ by the reactions with benzyl and allyl bromides is caused by the high reactivity of the carbanion ligand of [RCo(bpy)2]+ produced by the homolytic cleavage of the cobalt–carbon bond of cis-[R2Co(bpy)2]+, which undergoes the exchange, coupling, and cross-coupling reactions with benzyl and allyl groups of the bromides. Based on the
OXIDATION OF<i>cis</i>-DIALKYLCOBALT(III) COMPLEXES BY OXYGEN. ACTIVATION OF OXYGEN BY PERCHLORIC ACID
作者:Shunichi Fukuzumi、Kunio Ishikawa、Toshio Tanaka
DOI:10.1246/cl.1986.1
日期:1986.1.5
The effects of protons on the reactions of cis-dialkylcobalt(III) complexes, cis-[R2Co(bpy)2]ClO4 (R = Me, Et, PhCH2; bpy = 2,2′-bipyridine), with oxygen are reported. Oxygen is shown to be activated in the presence of perchloric acid by forming hydroperoxonium ion which has a much stronger oxidizing ability than oxygen.
The Relationships between the Formation Constants of 2,2′-Bipyridine Metal(II) Complexes and the Donor Numbers of Solvents
作者:Yuriko Abe、Goro Wada
DOI:10.1246/bcsj.60.1936
日期:1987.5
The complexformation constants of cobalt(II) or zinc(II) with 2,2′-bipyridine (bpy) were determined spectrophotometrically in various solvents. The values of logK1, logK2, and logK3 for the Co(II) complexes obtained were 4.06±0.06, 3.09±0.04, and 1.15±0.02 respectively in dimethyl sulfoxide, while those of logK1 for the Zn(II)–bpy complexes were 6.27±0.10, 4.14±0.01, 4.71±0.03, and 3.44±0.12 in trimethyl
钴 (II) 或锌 (II) 与 2,2'-联吡啶 (bpy) 的络合物形成常数在各种溶剂中通过分光光度法测定。在二甲基亚砜中获得的Co(II)配合物的logK1、logK2和logK3值分别为4.06±0.06、3.09±0.04和1.15±0.02,而Zn(II)-bpy配合物的logK1值为6.27在磷酸三甲酯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺和二甲亚砜中分别为 ±0.10、4.14±0.01、4.71±0.03 和 3.44±0.12。发现当溶剂化金属离子和bpy配合物在溶剂中都是八面体时,bpy配合物的形成常数的对数与溶剂的供体数之间存在线性关系。
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