Thermodynamic and spectroscopic study of the binding of dimethyltin(IV) by citrate at 25°C

Michelangelo Scopelliti, Alberto Pettignano, Lorenzo Pellerito, Paola Cardiano, Ottavia Giuffrè, Silvio Sammartano

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Abstract

Thermodynamic (potentiometric and calorimetric) and spectroscopic (1H NMR, 119Sn M¨ossbauer)studieswere performed in aqueous solution in order to characterize the interaction of dimethyltin(IV)cation with citrate ligand. Six species {(CH3)2Sn(cit)−; [(CH3)2Sn]2(cit)22−; (CH3 )2Sn(cit)H0; (CH3)2Sn(cit)OH2−; [(CH3)2Sn]2(cit)OH0; [(CH3)2Sn]2(cit)(OH)2−} were found. All the species formed in this system are quite stable and formation percentages are fairly high. For example, at pH = 7.5 and C(CH3)2Sn = Ccit = 10 mmol l−1, % for [(CH3)2Sn]2(cit)(OH)2− and (CH3)2Sn(cit)OH2− species reaches 65%. Overall thermodynamic parameters obtained show that the main contribution tostability is entropic in nature. Thermodynamic parameters were discussed in comparison with asimple tricarboxylate ligand (1,2,3-propanetricarboxylate). Two empirical relationships were derivedfrom thermodynamic formation parameters. Spectroscopic results fully confirm the speciation modeldefined potentiometrically and showthe mononuclear species to have an eq-(CH3)2Tbp structurewithdifferent arrangements around the metal, while for [(CH3)2Sn]2(cit)(OH)2− there are two different Sn(IV) environments, namely trans-(CH3)2 octahedral and cis-(CH3)2 Tbp.
Original languageEnglish
Pages (from-to)425-435
Number of pages11
JournalApplied Organometallic Chemistry
Volume20 (7)
Publication statusPublished - 2006

All Science Journal Classification (ASJC) codes

  • General Chemistry
  • Inorganic Chemistry

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