Std. thermodynamic functions for the equil. [CuL2]2+ + X- .dblharw. [CuL2X]+ where L = en and H2N(CH2)3NH2 (tn) and for [CuL]2+ + X- .dblharw.[[CuLX]+ where L = triethylenetetramine (trien), H2N(CH2)2NH(CH2)3NH(CH2)2NH2 (2,3,2-tet), and H2N(CH2)3NH(CH2)3NH(CH2)3NH2 (3,3,3-tet) and X = I, SCN, and N3 were detd. in MOH at 25°. Equil. consts. were detd. spectrophotometrically. Heats of reaction were detd. directly by calorimetric titrn. Enthalpies of formation are all pos. or only slightly neg., while entropies are largely pos. For each Cu(II) polyamine complex the enthalpy (ΔH°) and entropy (ΔS°) changes decrease in the order N3- > I- > SCN-. With the same inorg. anion ΔH° and ΔS° decrease in the order [Cu-(en)2]2+ > [Cu(trien)]2+ ∼ [Cu(2,3,2-tet)]2+ > [Cu(tn)2]2+ > [Cu(3,3,3-tet)]2+.

Formation of five-coordinate cations between copper(II) polyamine complexes and inorganic anions. Standard thermodynamic functions in methanol at 25.deg.

FABBRIZZI, LUIGI;
1972-01-01

Abstract

Std. thermodynamic functions for the equil. [CuL2]2+ + X- .dblharw. [CuL2X]+ where L = en and H2N(CH2)3NH2 (tn) and for [CuL]2+ + X- .dblharw.[[CuLX]+ where L = triethylenetetramine (trien), H2N(CH2)2NH(CH2)3NH(CH2)2NH2 (2,3,2-tet), and H2N(CH2)3NH(CH2)3NH(CH2)3NH2 (3,3,3-tet) and X = I, SCN, and N3 were detd. in MOH at 25°. Equil. consts. were detd. spectrophotometrically. Heats of reaction were detd. directly by calorimetric titrn. Enthalpies of formation are all pos. or only slightly neg., while entropies are largely pos. For each Cu(II) polyamine complex the enthalpy (ΔH°) and entropy (ΔS°) changes decrease in the order N3- > I- > SCN-. With the same inorg. anion ΔH° and ΔS° decrease in the order [Cu-(en)2]2+ > [Cu(trien)]2+ ∼ [Cu(2,3,2-tet)]2+ > [Cu(tn)2]2+ > [Cu(3,3,3-tet)]2+.
File in questo prodotto:
Non ci sono file associati a questo prodotto.

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11571/465133
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus ND
  • ???jsp.display-item.citation.isi??? ND
social impact