Kinetics and Mechanism for Formation of Olefin Complexes in the Reaction between Palladium(II) and Maleic Acid.

Inorg Chem

Inorganic Chemistry 1, Chemical Center, Lund University, P.O. Box 124, S-221 00 Lund, Sweden.

Published: October 1998

Complex formation between Pd(H(2)O)(4)(2+) and maleic acid (H(2)A) has been studied at 25 degrees C and 2.00 M ionic strength in acidic aqueous solution. Reaction takes place with 1:1 stoichiometry. The kinetics has been followed by use of stopped-flow spectrophotometry under pseudo-first-order conditions with maleic acid in excess. In the concentration ranges 0.01 C where, in addition, both steps contain contributions from parallel reactions. The amplitude of the first phase increases with increasing [H(2)A](tot) and with decreasing [H(+)]. Multiwavelength global analysis of the kinetic traces and the UV-vis spectral changes suggest that a monodentate oxygen-bonded hydrogen maleate complex, [Pd(H(2)O)(3)OOCCH=CHCOOH](+), B, with stability constant K(2) = 205 +/- 40 M(-)(1) is formed as an intermediate in this first step via two parallel reversible reactions in which Pd(H(2)O)(4)(2+) reacts with maleic acid and hydrogen maleate, respectively. In the following step, B --> C, slow intramolecular ring closure with a rate constant of 0.8 +/- 0.1 s(-)(1) at 25 degrees C gives the reaction product C, which is concluded to be a 4.5-membered olefin-carboxylato chelate complex on the basis of stoichiometry and UV-vis/NMR spectra. Parallel and irreversible attack by maleic acid and hydrogen maleate acting as olefins on the intermediate B also leads to formation of C. C is stable for at least 20 h for concentrations of

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http://dx.doi.org/10.1021/ic980072fDOI Listing

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