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  • 1985-1989  (3)
  • Organic Chemistry  (3)
  • 1
    ISSN: 0268-2605
    Keywords: Organotin ; 2-mercaptoethanesulfonates ; solid state ; solution ; Mössbauer spectra ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The configuration of the bonding environment of tin in the complexes [R2Sn(SCH2CH2SO3)2]2- (R = Me, Ph) and [Me3Sn(SCH2CH2SO3)]- has been determined to be tetrahedral both in the solid state and in aqueous solution (for the methyl derivatives). The coordination number of tin increases to five in aqueous solutions for the Me2Sn(IV) complexes in Hepes buffer (N-2-hydroxyethylpiperazine-N′-2-ethanesulfonic acid; at least in fivefold excess, at pH 7.4) due to coordination by the tertiary amino nitrogen atom. No effect is detected due to the surfactant 2-hydroxypropylcellulose concerning both coordination to tin and influence on the Mössbauer parameters. The stoichiometry of mixed complex formation in aqueous solution of Me2Sn(IV), 2-mercaptoethanesulfonate and Hepes is 1:2:1, according to a procedure of ‘Mössbauer titration’. All complexes in aqueous solution undergo slow lysis of the tin-sulfur bonds. Structural assignments have been generally effected on the basis of the magnitude of experimental values of Mössbauer nuclear quadrupole splittings, measured at 77 K for both solid and frozen aqueous absorbers, and comparison with data calculated by the point-charge model approach.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0268-2605
    Keywords: organotin ; amino-acid ; cysteine ; penicillamine ; Mössbauer ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The bonding and the configuration of the tin environment in the title compounds {R2Sn[SCH2CH(NH3+)COO-]2 and R2Sn[SC(CH3)2CH(NH3+)COO-]2, indicated in the following as R2Sn(cysH)2 and R2Sn(penH)2 respectively} has been investigated through the determination of the Mössbauer-Zeeman spectra of Ph2Sn(cysH)2 and Ph2Sn(penH)2 in the solid state, and through conventional Mössbauer spectroscopy of Me2Sn(penH)2 in the solid state as well as of Me2Sn(cysH)2 and Me2Sn(penH)2 in aqueous solution (frozen). The treatment of the data by the pointcharge model approach suggested the general occurrence of a tetrahedral C2SnS2 core. In aqueous Hepes buffer, a tertiary amino nitrogen atom has been observed to coordinate tin in Me2Sn(cysH)2 and Me2Sn(penH)2, with formation of trigonal bipyramidal tin environments. The latter solutions undergo slow decomposition reactions at room temperature. From (Me2SnS)3 occurs, as well as formation of soluble complex species in the presence of glycylglycine; Me2Sn(penH)2 appears to undergo a slow desulfuration reaction.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Applied Organometallic Chemistry 2 (1988), S. 417-425 
    ISSN: 0268-2605
    Keywords: organotin ; cysteinate ; murine P-388 leukaemia ; infrared spectra ; NMR spectra ; Mössbauer spectra ; structures ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The in vivo activity of some R2Sn-L-cysteinate complexes (R = Me, Et, n-Bu) against murine P-388 leukaemia has been tested. Only the Et2Sn(IV) complex showed a marginal positive effect. Trigonal bipyramidal tin environments with two carbon (R) atoms and the sulfur atom in the equatorial plane and oxygen (carboxylate) and nitrogen (NH2) in apical positions have been proposed for the solid compexes (R = Me, Et, n-Bu, Ph) on the basis of experimental Mössbauer parameters and infrared (IR) data. Aqueous solutions of the Me2Sn—L-cysteinate have been studied by IR, 1H NMR and 119Sn Mössbauer spectroscopy (in frozen solution) at different pH values to identify the Me2Sn(IV) species present. At pH 〉 2 the dimethyltin aquocation is complexed by the ionized sulfhydryl group of L-cysteine to form a five-coordinated species. With increasing pH values, NH3+ is deprotonated and a chelate is proposed with both the sulfhydryl and the amino group bonded to tin, one water molecule or (at still higher pH values) one hydroxyl ion occupying the fifth coordination site of a trigonal bipyramid around tin. Finally at pH 〉 10 the NH2 group is substituted by a hydroxyl ion.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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