Oxidation – Reduction Reactions of Tetrachloroaurate(III) Anion with Triphenyl Derivatives of Group V Elements
Oxidation – Reduction Reactions of Tetrachloroaurate(III) Anion with Triphenyl Derivatives of Group V Elements
复制标题
四氯金酸(III)阴离子与V族元素三苯基衍生物的氧化-还原反应
DOI：
10.1002/hlca.19730560724
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发表时间：
1973
影响因子：
1.8
通讯作者：
Gerald P. Jun. Fenske
中科院分区：
文献类型：
--
作者：
R. Roulet;N. Lan;W. Mason;Gerald P. Jun. Fenske
在非水溶液中，L（L = PPh_3，AsPh_3，SbPh_3）对四氯金酸（III）阴离子的还原是定量的。产物是金（I）-配合物AuClL（L = AsPh 3，SbPh 3）和Au（PPh 3）+2以及相应的氧化产物LCl 2。动力学研究表明，AuCl−1和L.此外，在二氯甲烷中发现了独立于PPh 3的路径。这些数据被解释为涉及AuCl−4还原为AuCl−2，然后平衡形成AuClL（L = AsPh 3和SbPh 3）的机制。对于PPh 3，数据与氯化物被PPh 3置换得到AuCl 3 PPh 3，随后被第二摩尔PPh 3快速还原一致。本文报道了几种Au（I）配合物的平衡形成常数。
The reduction of the tetrachloroaurate (III) anion by L (L = PPh3, AsPh3, SbPh3) is quantitative in non-aqueous solution. The products are the gold(I)-complexes AuClL (L = AsPh3, SbPh3) and Au(PPh3)+2 together with the corresponding oxidation product LCl2. Kinetic studies show that the reactions are first order in AuCl−1 and L. In addition a path independent of PPh3 was found in dichloromethane. These data are interpreted in terms of mechanisms which involve reduction of AuCl−4 to AuCl−2 followed by equilibrium formation of AuClL for L = AsPh3 and SbPh3. For PPh3, the data are consistent with a chloride replacement by PPh3 to give AuCl3 PPh3, which is followed by a rapid reduction by a second mole of PPh3. Equilibrium formation constants are reported for several Au(I) complexes.