Complex Formation in the Ternary System Tl(III)-CN(-)-Cl(-) in Aqueous Solution. A (205)Tl NMR Study |
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Authors: | Berg Katja E Blixt Johan Glaser Julius |
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Institution: | Department of Chemistry, Inorganic Chemistry, The Royal Institute of Technology (KTH), 100 44 Stockholm, Sweden. |
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Abstract: | The existence of mixed complexes of the general formula Tl(CN)(m)()Cl(n)()(3)(-)(m)()(-)(n)() (m + n = 4) in aqueous solution containing 3 M ionic medium {(H(+)+Li(+)),ClO(4)(-)} has been established by means of (205)Tl NMR. All six ternary complexes have been identified, and their compositions, chemical shifts, (205)Tl-(13)C spin-spin coupling constants, and peak integrals were determined and used to calculate the stability constants, beta = Tl(CN)(m)()Cl(n)()(3)(-)(m)()(-)(n)()]/{Tl(3+)]CN(-)](m)()Cl(-)](n)()}. Very good agreement was obtained between the equilibrium constants determined in this work and those estimated by a theoretical formula using the stability constants for the binary complexes and a statistical factor. Specific interaction coefficients have been calculated for the Tl(CN)(m)()(3)(-)(m)() (1 = m = 4) complexes. Some interesting correlations were found for the obtained NMR parameters. The stepwise formation constants for addition of one cyanide ligand, log K(CN), show linear dependence on both the spin-spin coupling constants, (1)J((205)Tl-(13)C), and the chemical shifts, delta(Tl). Also the interatomic distance, d(Tl-C), is linearly correlated to the spin-spin coupling constant. The correlations are discussed in terms of the Ramsey equation, involving bond properties, stereochemistry, and stability of the complexes. Since (1)J((205)Tl-(13)C) also shows linear dependence on the Tl-CN force constant, it is concluded that the above correlations reflect the Tl-CN bond strength. Thus, the most important factor contributing to the thermodynamic stability of the complexes is the enthalpy term, dominated by formation of very strong sigma-bonds between cyanide and thallium. These trends may prove useful for spectral/structural assignments but also for estimation of metal-to-ligand bond distances and stability constants for complexes which exist only in low concentration. |
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