On April 21, 1994, Schmuelling, Michael; Ryabov, Alexander D.; van Eldik, Rudi published an article.COA of Formula: C5H5NO3S The title of the article was To what extent can the Pt-C bond of a metallacycle labilize the trans position? A temperature- and pressure-dependent mechanistic study. And the article contained the following:
The orthoplatinated complexes [Pt{C6H3X(CH2NMe2)}(NC5H4SO3-3)(H2O)] (X = H 1a or 3-MeO 1b) were designed for mechanistic studies in H2O. The aqua ligand is located trans to the Pt-C bond of the Ph group which lies in the Pt(II) coordination plane. The rates of substitution of the aqua ligand by nucleophiles (Nu) (Cl-, Br-, I-, N3-, SCN-, thiourea, N,N’-dimethylthiourea or N,N,N’,N’-tetramethylthiourea) were studied as a function of concentration, pH, temperature, and pressure by using a stopped-flow technique. The pKa value of the aqua ligand in 1a is 9.75 ± 0.505 and the observed pseudo-first-order rate constants for the substitution reaction are given by kobs = k1[Nu] + k-1. The k-1 term arises from the reverse solvolysis reaction and is insignificant for stronger, S-donor nucleophiles. The values of k1 are ∼4 orders of magnitude higher than the corresponding rate constants for anation reactions of [Pt(dien)(H2O)]2+ (dien = diethylenetriamine) and close to the rate constants for anation of [Pd(dien)(H2O)]2+. The effect is largely due to a strong decrease in ΔH⧧, ΔS⧧ and ΔV⧧, clearly shows that the substantial rate increase is not associated with a changeover in mechanism and that the substitution process is still associative. The experimental process involved the reaction of Pyridine-3-sulfonic acid(cas: 636-73-7).COA of Formula: C5H5NO3S
The Article related to substitution kinetics nucleophile aminomethylplatinum complex, platinum aminomethyl substitution kinetics nucleophile, reactivity aminomethylplatinum complex nucleophile, reaction mechanism aminomethylplatinum complex nucleophile substitution, bond platinum carbon lability aminomethylplatinum metallacycle and other aspects.COA of Formula: C5H5NO3S