Abstract
Kinetics for complex formation between Pd(H2O)42+ and thioethers of largely varying electronic and steric properties, viz. MeSCH2COOH, (n-Pr)2S, EtSCH2CH2OH, S(CH2CH2CH2OH)2, S(CH2CH2OH)2, EtSCH2COOH, S(CH2COOH)2, S(CH2CH2COOH)2, (i-Pr)2S, (s-Bu)2S, (t-Bu)2S, and protonated thiomorpholine, S(C2H4)2NH2+, has been studied by use of stopped-flow spectrophotometry in an acidic aqueous medium. Second-order rate constants k1298 are 1.61 × 104, 8.0 × 104, 3.79 × 104, 3.69 × 104, 2.21 × 104, 1.84 × 104, 1.91 × 103, 1.34 × 104, 1.52 × 104, 7.75 × 103, 900, and 5.2 × 103 M-1 s-1, respectively. The reactivity toward Pd(H2O)42+ of all thioethers studied so far can be described as a function of their σ-donor properties as expressed by the sum of the Taft constants, ∑σ*, and their steric requirements as defined by cone angles, θ, by use of the equation: log k1 = (9.9 ± 0.3) − (0.67 ± 0.05)∑σ* − (0.059 ± 0.003)θ. Similarly, second-order rate constants k298 reported previously for reactions between thioethers and Pd(die...
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