Chemically catalyzed disproportionation of tris(2,2'-bipyridine)ruthenium(2+)
Chemically catalyzed disproportionation of tris(2,2'-bipyridine)ruthenium(2+)
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三(2,2-联吡啶)钌的化学催化歧化反应(2 )
DOI：
10.1021/ic50178a083
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发表时间：
1977
影响因子：
4.6
通讯作者：
T. Meyer
中科院分区：
文献类型：
--
作者：
J. Nagle;R. C. Young;T. Meyer
虽然Tanaka证明了在N，N-二甲基甲酰胺中Co（en）33+和高氯酸根离子之间的离子对形成常数大于在纯水溶液中的离子对形成常数，但尚不清楚高氯酸根对还原速率的影响是归因于简单盐效应还是Co（en）33+和高氯酸根之间的离子对形成。机制在二甲基甲酰胺水溶液中，钒（II）还原Co（en）~（33+）的反应与在水溶液中的反应一样，都是通过外层机制进行的。[16]值得注意的是，Co（en）33+和钒（II）之间的外层电子转移反应在加入TV后加速。而在丙酮溶液中，Co（phen）32+与Co（phen）33+之间的电子转移速率随丙酮含量的增加而降低。[17]对于钒（II）还原Co（Cl）（NH3）52+，Taube、18 Linck、13和Sykes提出了外层机制。19发现钒（II）还原Co（Cl）（NH3）52+的速率随着TV摩尔分数的增加而增加。N-二甲基甲酰胺（表IV）。N，N-二甲基甲酰胺还原Co（Cl）（NH_3）_5 ~（2+）和Co（N_3）（NH_3）_5 ~（2+）的作用差异可能与机理不同有关。本文提出了水溶液中钒（II）还原Co（N_3）（NH_3）_5 ~（2+）的内球电子转移机理和前体络合物的形成为速率控制步骤。20
Though Tanaka demonstrated that the ion-pair formation constant between Co (en) 33+ and perchlorate ions in N, N-dimethylformamide is larger than that in a pure aqueous solution, 15 it is not clear whether the effect of perchlorate on the reduction rates is attributed to the simplesalt effect or the ion-pair formation between Co (en) 33+ and perchlorate. Mechanism. The reduction of Co (en) 33+ by vanadium (II) in aqueous solutions of MfV-dimethylformamide must proceed via an outer-sphere mechanism as well as in the case of in aqueous solution. 16 It is noteworthy that the outer-sphere electron-transfer reaction between Co (en) 33+ and vanadium (II) is accelerated upon addition of TV. TV-dimethylformamide, whereas the rate of electron-transfer between Co (phen) 32+ and Co (phen) 33+ in aqueous acetone decreases with the increase in the content of acetone. 17 For the reduction of Co (Cl)(NH3) 52+ by vanadium (II), an outer-sphere mechanism was proposed by Taube, 18 Linck, 13 and Sykes. 19 It was found that the rate of reduction of Co (Cl)(NH3) 52+ by vanadium (II) increases with the increase in the mole fraction of TV. fV-dimethylformamide (Table IV). The difference between the effectof TV, 7V-dimethylformamide in the reductions of Co (Cl)(NH3) 52+ and Co (N3)(NH3) 52+ may be related to a difference of mechanism. The inner-sphere electron-transfer mechanism and the formation of the pre-cursor complex as the rate-determining step have been pro-posed for the reduction of Co (N3)(NH3) 52+ by vanadium (II) in aqueous solution. 20