Substituent effects of cis-dioxobis(dithiocarbamato) molybdenum(VI) on redox properties: redox potentials for one-electron reduction and second-order rate constants for oxygen atom transfer
作者:Kei Unoura、Akira Yamazaki、Akira Nagasawa、Yoshikiyo Kato、Hiroki Itoh、Hideaki Kudo、Yutaka Fukuda
DOI:10.1016/s0020-1693(97)05813-1
日期:1998.3
The electrochemical properties of a series of cis-dioxobis(dithiocarbamato)molybdenum(VI) complexes [MoO2(RR′dte)2] (RR′dte = N,N-disubstituted dithiocarbamate) and the oxygen atom transfer reactions between [MoO2(RR′dte)2] and PPh3 in 1,2-C2H4Cl2 at 25°C are systematically investigated. A good correlation between logarithmic values of second-order rate constants k1 of the oxygen atom transfer reactions
一系列顺式-二氧杂双(二硫代氨基甲酸酯)钼(VI)的电化学性质[MoO 2(RR'dte)2 ](RR'dte = N,N-二取代的二硫代氨基甲酸酯)和[MoO 2之间的氧原子转移反应对25℃下1,2-C 2 H 4 Cl 2中的(RR'dte)2 ]和PPh 3进行了系统研究。氧原子转移反应的二阶速率常数k 1的对数值与[MoO 2 OP 2 RR'dte)2 ] 0的氧化还原电势E °'具有良好的相关性1个耦合观察到在大范围内的ķ 1(0.012至0.61米每秒2); log k 1的值随着E 0的增加而线性增加。对于[MoO 2(Bz 2 dte)2 / PPh 2 [MoO 2(Ph 2 dte)2 ] / PPh 1和[MoO 2(BzPhdte)2 ] PPh 1系统,可以准确观察到与相关线的偏离。负激活熵(ΔS '= -114 J mol +1 K +1对于[MoO 2(Et