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Potentiometric measurements
M. Cesario, J. Guilhem, E. Pascard, E. Anklam, J. M. Lehn and
M. Pietraskiewicz, Helv. Chim. Acta, 1991, 74, 1157; (d )
J. Bkouche-Waksmann, J. Guilhem, E. Pascard, B. Alpha,
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All the pH metric measurements (pH = Ϫlog [Hϩ]) were carried
out in degassed 0.1 mol dmϪ3 NMe4Cl solutions, at 298.1 K, by
using previously reported equipment and procedures.33 The
combinated Ingold 405 S7/120 electrode was calibrated as a
hydrogen concentration probe by titrating known amounts of
HCl with CO2-free NMe4OH solutions and determining the
equivalent point by the Gran’s method34 which allows
determination of the standard potential E o, and the ionic
product of water (pKw = 13.83(1) at 298.1 K in 0.1 mol dmϪ3
NMe4Cl). At least three potentiometric titrations were per-
formed for each system in the pH range 2.5–11. A ligand
concentration of [L] = 1 × 10Ϫ3 mol dmϪ3 and a metal concen-
tration of [M] = 0.8[L] were adopted in the complexation
experiments (L = L or L1). Due to the high stability of the
Cu() complexes with L1, competition between protonation of
the free ligands and complex formation is not significant
enough to derive the values of the stability constants, and the
use of EDTA as an auxiliary ligand was necessary. The relevant
emf data were treated by means of the computer program
HYPERQUAD35 which furnished the equilibrium constants
reported in Tables 1 and 4.
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21 (a) C. Bazzicalupi, A. Bencini, V. Fusi, C. Giorgi, P. Paoletti and
B. Valtancoli, Inorg. Chem., 1998, 37, 941; (b) C. Bazzicalupi,
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A. Bianchi, C. Giorgi, V. Fusi, B. Valtancoli, M. A. Bernardo and
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A. Bencini, M. A. Bernardo, A. Bianchi, V. Fusi, C. Giorgi, F. Pina
and B. Valtancoli, Eur. J. Inorg. Chem., 1999, 1911.
22 (a) C. Bazzicalupi, A. Bencini, S. Ciattini, C. Giorgi, A. Masotti,
P. Paoletti, B. Valtancoli, N. Navon and D. Meyerstein, J. Chem.
Soc., Dalton Trans., 2000, 2383; (b) C. Bazzicalupi, A. Bencini,
A. Bianchi, C. Giorgi, V. Fusi, A. Masotti, B. Valtancoli, A. Roque
and F. Pina, Chem. Commun., 2000, 561; (c) A. Bencini, A. Bianchi,
C. Lodeiros, A. Masotti, A. J. Parola, J. S. Melo, F. Pina and
B. Valtancoli, Chem. Commun., 2000, 1639; (d ) A. Bencini,
A. Bianchi, V. Fusi, C. Giorgi, A. Masotti and P. Paoletti, J. Org.
Chem., 2000, 65, 7686; (e) C. Lodeiro, A. J. Parola, F. Pina,
C. Bazzicalupi, A. Bencini, A. Bianchi, C. Giorgi, A. Masotti and
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A. Bencini, E. Berni, A. Bianchi, C. Giorgi, V. Fusi, B. Valtancoli,
C. Lodeiro, A. Roque and F. Pina, Inorg. Chem., 2001, 40, 6172; (g)
P. Arranz, C. Bazzicalupi, A. Bencini, A. Bianchi, S. Ciattini,
P. Fornasari, C. Giorgi and B. Valtancoli, Inorg. Chem., 2001, 40,
6383.
Acknowledgements
This work has been supported by the Italian Ministero
dell’Università e della Ricerca Scientifica e Tecnologica
(MURST, Rome) within the program COFIN 2000. We thank
the “Centro Interdipartimentale di Spettrometria di Massa”
(University of Florence) for ESI mass spectra.
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