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Kinetics of the Displacement of Cyclobutane-1,1-dicarboxylate from Diammine(cycxlobutane-1,1-dicarboxylato)platinum(II) in Aqueous Solution

DOI: 10.1039/DT9880002135

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2135 - 2140 (1988)

Update date:2022-08-28

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Authors:

Canovese, LucianoCanovese, Luciano

Cattalini, LucioCattalini, Lucio

Chessa, GavinoChessa, Gavino

Tobe, Martin L.Tobe, Martin L.

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Article abstract of DOI:10.1039/DT9880002135

The displacement of 1,1-cyclobutanedicarboxylate (cbdca2-) from has been studied in aqueous solution.In the presence of acid the process resembles the successive displacement of two monodentate carboxylates.The first (ring-opening) stage follows the rate law kobs = (k0 + k1K0+>)(1 + K0+>)-1, k0 = 8 x 1E-5 s-1, K0 = 0.6 dm3mol-1, k1 = 8.0 x 1E-4 s-1 at 25 deg C, while the second follows the simple relationship kobs = k+>, k = 1.61 x 1E-4 dm3mol-1s-1 at 25 deg C.In the absence of acid and other nucleophiles the complex is inert and in the presence of chloride the displacement of ligand follows a first-order dependence on ->, kobs = kCl = ->.At 80 deg C, kCl = 1.32 x 1E-4 dm3mol-1s-1.The chelate differs from the bis-monodentate carboxylate species in the great importance of the reverse, ring-closing process, which can be prevented in the presence of acid.

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