A kinetic study of HgII and CdII catalyzed solvolysis of complexes of the type [Pd(AAA)X]+ (AAA = 1,1,7,7-tetraethyldiethylenetriamine (Et4dien) and 4-methyl-1, 1,7,7-tetraethyldiethylenetriamine (MeEt4 dien); X = Cl, Br, I) has been carried out in methanol at 25° C. The first-order dependence of the reaction rate on [M++] is explained in terms of a solvent attack on a labile binuclear adduct of the
Volumes of activation for the anation of Pd(II) substituted dien complexes by chloride ion in aqueous solution. A high pressure stopped-flow instrument for studying the kinetics of fast reactions under pressure
作者:R. Van Eldik、D.A. Palmer、R. Schmidt、H. Kelm
DOI:10.1016/s0020-1693(00)83732-9
日期:1981.1
Abstract The kinetics of anation of Pd(1,1,7,7-Et 4 dien)OH 2+ 2 and Pd(1,1,4-Et 3 dien)OH 2+ 2 by chloride ion were studied under pressures up to 1 kbar using a high pressure stopped-flow system. The construction and testing of the latter system are discussed in detail. The rate and activation parameters for the above reactions are: k(25 °C) = 4.2 ± 0.1 and 1558 ± 68 M −1 sec −1 ; ΔH≠ = 13.4 ± 0.4
Evidence for a strong labilization effect by co-ordinated sulphite in amine complexes of palladium(II)
作者:G. Mahal、R. van Eldik
DOI:10.1039/c39870000328
日期:——
Acidification of a chelated amine sulphito complex of palladium(II) to pH <6 results in dechelation and complete loss of the co-ordinatedamine ligand in the presence of an excess of sulphite; this process is completely reversible on increasing the pH(>8) and reproduces the amine sulphito complex.