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Modelling the Hydrolysis of Mixed Mono-, Di- and Trimethyltin(IV) Complexes in Aqueous Solutions

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Abstract

The formation of mixed hydrolytic species obtained by the interaction of dimethyltin(IV) {(CH3)2Sn2+ or DMT or M22+} with the monomethyltin(IV) (CH3Sn3+ or MMT or M13+) and trimethyltin(IV) {(CH3)3Sn+ or TMT or M3+} cations was studied in aqueous solutions of NaNO3, at I = 1.00 ± 0.05 mol·dm−3 and T = (298.15 ± 0.1) K, by the potentiometric technique. The formation of several mono- and polynuclear hydrolytic mixed species was observed in the two mixed systems. For the (M1) p (M2) q (OH) r mixed species we have: (p, q, r) = (1, 1, 3), (1, 1, 4), (1, 1, 5), (2, 1, 5), (2, 1, 7), (1, 3, 6) and (2, 3, 11); for (M2) p (M3) q (OH) r : (p, q, r) = (1, 1, 2), (1, 1, 3), (1, 2, 3), (1, 2, 4), (2, 1, 4), (3, 1, 4) and (3, 1, 5). The stability of these species, expressed by the following general equilibrium:

$$ p {\text{Mi}}^{n + } + q {\text{Mj}}^{j + } + r {\text{OH}}^{-} \rightleftharpoons \left( {\text{Mi}} \right)_{p} \left( {\text{Mj}} \right)_{q} \left( {\text{OH}} \right)_{r}^{{\left( {np + jq{-}r} \right)}} \quad \beta_{pqr}^{\text{OH}} $$

can be modelled by the empirical relationship that depends on the stoichiometry of the species:

$$ \log_{10} \beta_{pqr}^{\text{OH}} = a_{1} p + a_{2} q + a_{3} r {-} y $$

For the (M1) p (M2) q (OH) r species: a 1 = 6.98, a 2 = 2.73, a 3 = 9.93 and y = 1.14, while for the (M2) p (M3) q (OH) r species: a 1 = 5.03, a 2 = 1.00, a 3 = 8.04 and y = 1.71. By using the equilibrium constant X pqr relative to the formation reactions:

$$ p\left( {{\text{M}}1} \right)_{{\left( {p + q} \right)}} \left( {\text{OH}} \right)_{r} + q\left( {{\text{M}}2} \right)_{{\left( {p + q} \right)}} \left( {\text{OH}} \right)_{r} \rightleftharpoons \left( {p + q} \right)\left( {{\text{M}}1} \right)_{p} ({\text{M}}2)_{q} \left( {\text{OH}} \right)_{r} $$

and

$$ p({\text{M}}2)_{{\left( {p + q} \right)}} \left( {\text{OH}} \right)_{r} + q({\text{M}}3)_{{\left( {p + q} \right)}} \left( {\text{OH}} \right)_{r } \rightleftharpoons \left( {p + q} \right)\left( {{\text{M}}2} \right)_{p} ({\text{M}}3)_{q} \left( {\text{OH}} \right)_{r} $$

we found that the formation of hetero-metal mixed species is thermodynamically favored and the extra stability can be expressed as a function of the difference in the stability of the parent homo-metal species. This leads, in turn, to a significant enhancement of hydrolysis. The general stability and extra stability behavior of mixed-metal (or organometal) species is discussed while also considering previous findings from this laboratory.

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Authors and Affiliations

  1. Dipartimento di Scienze Chimiche, Università di Messina, Viale Ferdinando Stagno d’Alcontres, 31-98166, Messina, (Vill. S. Agata), Italy

    Rosalia Maria Cigala, Francesco Crea, Concetta De Stefano & Silvio Sammartano

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  1. Rosalia Maria Cigala
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  2. Francesco Crea
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  3. Concetta De Stefano
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  4. Silvio Sammartano
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Correspondence to Rosalia Maria Cigala.

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Previous contributions to this series: Refs. 8, 10 and 11.

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Cigala, R.M., Crea, F., De Stefano, C. et al. Modelling the Hydrolysis of Mixed Mono-, Di- and Trimethyltin(IV) Complexes in Aqueous Solutions. J Solution Chem 44, 1611–1625 (2015). https://doi.org/10.1007/s10953-015-0367-4

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