Solvolysis and Complex Formation

For the N-bonded isomers, the Hg + can easily attack the free sulphur or selenium atoms of the ligands, so the equilibrium is displaced to the right and the rate law reduces to kexD = ki since ki for the spontaneous solvolysis is approximately 3 X 10 times smaller than kf for the mercury(ii)-accelerated one. For the sulphur-or selenium-bonded isomers on the other hand, the rate law (10) reduces to A e.xp = A i X[Hg +]. It should be noted that in this case the experiments cannot 

Cusumano, G. Guglielmo, and P. Marricchi, Inorg. Chim. Acta, 1978, 30, 29. 

Irradiation of [Pd(MeEt4dien)(N02)]+ in methanol solution using wavelengths in the charge-transfer and ligand-field regions causes linkage isomerization followed by parallel photosolvolysis and thermal solvolysis of the formed nitrito-complex  

Activation parameters for the anation by chloride of the sterically hindered [Pd(MeEt4dien)(OH2)] + have been determined using a newly developed high-pressure stopped-flow instrument for moderately fast reactions. A negative activation volume and a zero activation entropy are compatible with an associative mechanism, probably 7a. This study is the first in a series in which the effect of pressure on such relatively fast reactions will be studied. A summary of published and current work on pressure effects on the kinetics of sterically hindered palladium(ii) complexes by the Frankfurt group has appeared.  

Steric effects of bulky entering ligands have been studied using the classical [Pd(dien)(HaO)] + complex as the substrate  

---

Solvolysis and Complex Formation.— The mercury(ii)-accelerated solvolysis of a series of thiocyanato- and selenocyanato-complexes and their N-bonded linkage isomers can be described by Scheme 5, where X stands for the thio- or seleno-... 

---