Redox behavior of copper(II) and copper(I) complexes with tetradentate bis(pyridyl)-dithiaether and bis(pyridyl)-diaza ligands towards ruthenium ammine and bipyridyl complexes
作者:Keith M. Davies、Bardia Guilani
DOI:10.1016/s0020-1693(00)82124-6
日期:1987.3
complex, Cu- (pdto) 2+ , and a series of Ru(II) ammine and bipyridyl complexes have been studied kinetically in MES buffered 0.10 M LiCF 3 CO 2 . Values of the second- order rate constant, k 2 (M -1 s -1 ) are Ru(NH 3 )5 py 2+ , 3.8 × 10 4 ; Ru(NH 3 ) 5 isn 2+ , 1.4 × 10 4 ; Ru(NH 3 ) 4 - bpy 2+ , 2.0 × 10 3 ; cis -Ru(NH 3 ) 4 (isn) 2 2+ , 2.3 × 10 2 ; cis - Ru(bpy) 2 Cl 2 , 4.4 × 10 4 ; Ru(bpy) 2 C 2
摘要涉及1,8-双-(2-吡啶基)-3,6-二硫辛烷铜(II)配合物,Cu-(pdto)2+以及一系列Ru(II)氨基和联吡啶配合物的电子转移反应具有在MES缓冲0.10 M LiCF 3 CO 2中进行了动力学研究。二阶速率常数k 2(M -1 s -1)的值为Ru(NH 3)5 py 2+,3.8×10 4;Ru(NH 3)5为2+,1.4×10 4; Ru(NH 3)4-bpy 2+,2.0×10 3; 顺式-Ru(NH 3)4(isn)2 2+,2.3×10 2; 顺式-Ru(bpy)2 Cl 2,4.4×10 4; Ru(bpy)2 C 2 O 4,4.5×10 5; 在25.0°C的50%甲醇水溶液中。胺络合物的数据遵循log k 2和E°(Ru(III)/ Ru(II)还原电位)之间的线性自由能关系,表明存在外层机理。用Ru(bpy)2 Cl 2和Ru(bpy)2 C 2 O