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Reactivity of Neutral Nitrogen Donors in Planar d8 Metal Complexes. Part 1. The System dichloroplatinum(II) with Pyridines in Methanol. Effect of Basicity and Steric Hindrance

DOI: 10.1039/DT9940001805

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1805 - 1812 (1994)

Update date:2022-08-04

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Authors:

Bellicini, MarcelloBellicini, Marcello

Cattalini, LucioCattalini, Lucio

Marangoni, GiampaoloMarangoni, Giampaolo

Pitteri, BrunoPitteri, Bruno

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Article abstract of DOI:10.1039/DT9940001805

The kinetics of the forward and reverse steps of the process + am <-/-> (+) + Cl(-) (am = one of a number of pyridines and other heterocyclic nitrogen bases covering a wide range of basicity) has been studied in methanol at 25 deg C.Both forward and reverse reactions obey the usual two-term rate law observed in square-planar substitution.The second-order rate constants for the forward reactions, k2f, show only a slight dependence upon the nature of the entering pyridine, and steric hindrance due to the presence of one or two methyl groups in α position to the nitrogen markedly decreases the reactivity.The first- and second-order rate constants for the reverse reaction are very sensitive to the basicity of the leaving group and a plot of log k2r against the pKa of the conjugate acids of unhindered pyridines is linear with a slope of -0.56.Steric retardation for monosubstituted α-methylpyridines is relatively small.The equilibrium constants for these reactions have been determined from the ratio of the rate constants and a plot of log K against the pKa of the unhindered pyridines is linear with a slope of 0.58.The results are compared with data from the literature and discussed in terms of the reaction profile.

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