Speciation and Multinuclear NMR Spectroscopic Studies of Di- and Trimethyltin(IV) Moieties with MESNA in Aqueous Medium

Abstract

The interaction of Me2Sn(IV)2+ and Me3Sn(IV)+ with a prodrug, sodium 2-mercaptoethane sulfonate (HSCH2CH2SO3Na, MESNA) abbreviated as (HL), has been studied potentiometrically in aqueous solution (I = 0.1 mol·L−1 KNO3, 298 K). The concentration distribution of various species formed in the solution was studied with changes in pH (~3–11). A strong coordination of MESNA with metal through the S atom of thiol group has been found. In the Me2Sn(IV)–HL system, the species [Me2Sn(L)]+ (53.1–75.6%) is predominant at acidic pH (3.73 ± 0.02) and the species [Me2Sn(L)2OH]− (29.4–38.5%) is predominant at basic pH (10.32 ± 0.08). In contrast, for the Me3Sn(IV)+ system, [Me3SnL] (37.0–57.4%) is the major species at pH 7.65 ± 0.03 and [Me3Sn(OH)] (49.9–67.2%) and [Me3Sn(L)(OH)]− (30.2–46.5%) are the major species at pH 11.05 ± 0.01. However, at physiological pH (7.01 ± 0.32), in both (1:1) and (1:2) Me2Sn(IV)–HL systems, the species [Me2Sn(L)(OH)] (67.2–89.9%) is predominant, whereas for Me3Sn(IV)–HL (1:1) and (1:2) systems, [Me3Sn(OH)] (53.5%) and [Me3SnL] (56.8%) are the respective predominant species. In order to characterize the possible geometry of the proposed complex species, multinuclear (1H, 13C and 119Sn) NMR studies were carried out at different pHs. No polymeric species were detected in the experimental pH range.