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Enthalpic and Entropic Contributions in the reactions of Hydrogen, Copper(II), and Nickel(II) Ions with the Macrocycle 1,5,9,13-Tetra-azacyclohexadecane

DOI: 10.1039/DT9800001722

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1722 - 1725 (1980)

Update date:2022-08-24

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Authors:

Gallori, ElisabettaGallori, Elisabetta

Martini, EmilioMartini, Emilio

Micheloni, MauroMicheloni, Mauro

Paoletti, PieroPaoletti, Piero

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Article abstract of DOI:10.1039/DT9800001722

Enthalpies of protonation of 1,5,9,13-tetra-azacyclohexadecane (L1) have been determined by a continous titration calorimetric technique and the corresponding entropy values obtained by combination with the free-energy data.The stepwise enthalpies are all very similar, and are interpreted in terms of the ability of the amino-groups to behave independently of each other towards protons.The stability constants of the complexes (CuL1)2+ and(CuHL1)3+ have been determined by potentiometry at 25 deg C in o.5 mol dm-3 K.The enthalpies of formation of the copper(II) and nickel(II) complexes of L1 have been determined by batch microcalorimetry, and are discussed in terms of the unfavourable free-ligand conformation and the presence of hindered chelate rings in the complexes.Finally the stability of the (CuL1)2+ complex is compared with that of the corresponding complex with the acyclic ligand 4,8-diazaundecane-1,11-diamine; the greater stability of the former complex is attributed to a very favourable entropy term and to a slightly favourable enthalpy term.

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