Reactions of pentaammineruthenium complexes with 1,2- and 1,4-dicyanobenzene and cyanobenzamides: evidences of neighboring group participation
作者:Elia Tfouni、Antônio Marcos de Souza Macêdo、Luciana nunes Cardoso、Kleber Queiroz Ferreira、Érica Cristina de Oliveira、Zênis Novais da Rocha
DOI:10.1016/j.ica.2004.09.008
日期:2005.6
ino-1-oxo-isoindoline) are described. Oxidation of [Ru(NH 3 ) 5 L] 2+ , at 0 ⩽ pH ⩾ 6, is followed by hydrolysis of the coordinated nitrile to give amide complexes in which the amide is through the nitrogen, with pH-dependent rate constants. The estimated values of the rate constant of hydrolysis ( k obs ) at 25 °C are 2.9 × 10 −3 s −1 for [Ru(NH 3 ) 5 (1,4-dcb)] 3+ and 5.6 × 10 −3 s −1 for [Ru(NH
摘要腈键结合配合物[Ru(NH 3)5 L] 2+(L = 1,4-二氰基苯(1,4-dcb),1,2-二氰基苯)的光谱(UV-Vis和IR)和电化学行为(1,2-dcb)),[Ru(NH 3)5(NHC(OH)-bz-4-CN)] 3+,[Ru(NH 3)5(NHC(O)-bz-2-CN )描述了2+和[Ru(NH 3)5(NH(C)NHC(O)bz)] 3+(NH(C)NHC(O)-bz = 3-imino-1-oxo-isoindoline) 。在0⩽pH⩾6下,氧化[Ru(NH 3)5 L] 2+,然后水解配位的腈,得到酰胺络合物,其中酰胺通过氮,具有pH依赖的速率常数。对于[Ru(NH 3)5(1,4-dcb)] 3+和5.6×10 -3,在25°C时水解速率常数(k obs)的估计值为2.9×10 -3 s -1 pH值为4.65时[Ru(NH 3)5(1,2-dcb)] 3+的s