TY - JOUR
T1 - Solvent effects on the stability of mixed ligand complexes
AU - Yellin, N.
AU - Marcus, Y.
PY - 1974/6
Y1 - 1974/6
N2 - The effect of solvents on the equilibrium MX42- + Y- ⇋ MYX32- + X-, where M = Cd2+ or Hg2+ and X and Y = Cl-, Br-, I-, or CN-, has been studied by quantitative Raman spectrophotometry. This technique, employing LiClO4 as internal reference, permits the direct determination of the decrease in concentration of the tetrahedral MX42- due to the formation of MYX32-. The fraction [1 - α(MX42-)] is thus a direct measure of the solvent effect on the mixed complex stability. It is shown that bulk solvent properties are not relevant, and only solvent molecules in the immediate vicinity of the anionic complex have an effect on its stability. Selective solvation in this second coordination sphere is exhibited by several solvents, and water is not always the preferred solvent.
AB - The effect of solvents on the equilibrium MX42- + Y- ⇋ MYX32- + X-, where M = Cd2+ or Hg2+ and X and Y = Cl-, Br-, I-, or CN-, has been studied by quantitative Raman spectrophotometry. This technique, employing LiClO4 as internal reference, permits the direct determination of the decrease in concentration of the tetrahedral MX42- due to the formation of MYX32-. The fraction [1 - α(MX42-)] is thus a direct measure of the solvent effect on the mixed complex stability. It is shown that bulk solvent properties are not relevant, and only solvent molecules in the immediate vicinity of the anionic complex have an effect on its stability. Selective solvation in this second coordination sphere is exhibited by several solvents, and water is not always the preferred solvent.
UR - http://www.scopus.com/inward/record.url?scp=49549150681&partnerID=8YFLogxK
U2 - 10.1016/0022-1902(74)80072-2
DO - 10.1016/0022-1902(74)80072-2
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AN - SCOPUS:49549150681
SN - 0022-1902
VL - 36
SP - 1325
EP - 1330
JO - Journal of Inorganic and Nuclear Chemistry
JF - Journal of Inorganic and Nuclear Chemistry
IS - 6
ER -