Thermodynamic studies on the complexation of cobalt(II) with nitrogen donor ligands in dimethyl sulfoxide

被引:18
作者
Comuzzi, C [1 ]
Grespan, M [1 ]
Polese, P [1 ]
Portanova, R [1 ]
Tolazzi, M [1 ]
机构
[1] Univ Udine, Dipartimento Sci & Tecnol Chim, I-33100 Udine, Italy
关键词
cobalt(II); amines; complexes; thermodynamics; dimethylsulfoxide;
D O I
10.1016/S0020-1693(01)00513-8
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Co(II) complex formation with the N-donor ligands n-butylamine (n-but), diethylenetriamine (dien),N,N"-dimethyldiethylenetriamine (dmdien) and N,N,N',N",N"-pentamethyldiethylenetriamine (pmdien) has been studied at 298 K in the aprotic solvent dimethyl sulfoxide (dmso) in an ionic medium set to 0.1 mol dm(-3) with NEt4ClO4 in anaerobic conditions. Potentiometric. spectrophotometric and calorimetric measurements have been carried out to obtain the thermodynamic parameters for the systems investigated. Only mononuclear CoLj2+ complexes are formed (j = 1-3 for n-but;j = 1, 2 for then and dmdien; j = 1 for pmdien) where the triamines act prevalently as terdentate agents. All the complexes are enthalpy stabilized whereas the entropy changes counteract the complex formation. The results are discussed in term of different basicities and steric requirements of both the ligands and the complexes formed. Preliminary information on the different affinities of the complexes for dioxygen is reported. (C) 2001 Elsevier Science B.v. All rights reserved.
引用
收藏
页码:49 / 55
页数:7
相关论文
共 42 条
[1]  
AHRLAND S, 1978, CHEM NONAQUEOUS SO A, V5
[2]  
ARNAUDNEU F, 1994, CHEM SOC REV, P235
[3]  
ARNEK R, 1970, ARK KEMI, V32, P81
[4]   BASICITY OF N-SUBSTITUTED ANILINES AND PYRIDINE IN DIMETHYLSULFOXIDE [J].
BENOIT, RL ;
MACKINNON, MJ ;
BERGERON, L .
CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1981, 59 (10) :1501-1504
[5]   A H-1-NMR STUDY OF THE COMPLEX OF COBALT(II) WITH 2,5,8,11-TETRAMETHYL-2,5,8,11-TETRAAZADO IN AERATED AQUEOUS-SOLUTIONS [J].
BERTINI, I ;
MESSORI, L ;
GOLUB, G ;
COHEN, H ;
MEYERSTEIN, D .
INORGANICA CHIMICA ACTA, 1995, 235 (1-2) :5-8
[6]   IRON AND COBALT LACUNAR COMPLEXES AS DIOXYGEN CARRIERS [J].
BUSCH, DH ;
ALCOCK, NW .
CHEMICAL REVIEWS, 1994, 94 (03) :585-623
[7]   THERMODYNAMIC AND KINETIC ASPECTS OF THE BINDING REACTION OF MOLECULAR-OXYGEN ON CO(II) COMPLEXES IN AQUEOUS-SOLUTIONS [J].
CABANI, S ;
CECCANTI, N ;
TINE, MR .
PURE AND APPLIED CHEMISTRY, 1991, 63 (10) :1455-1464
[8]   Binding of molecular dioxygen to Co(II) complexes in aqueous solutions [J].
Cabani, S .
REACTIVE & FUNCTIONAL POLYMERS, 1996, 28 (02) :167-182
[9]   THERMODYNAMICS OF LANTHANIDE(III) COMPLEXATION WITH ETHYLENEDIAMINE IN DIMETHYL-SULFOXIDE [J].
CASSOL, A ;
DIBERNARDO, P ;
PORTANOVA, R ;
TOLAZZI, M ;
TOMAT, G ;
ZANONATO, P .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1992, (03) :469-474
[10]   Complexing ability of the trifluoromethanesulfonate complexes of the heavier lanthanides(III) towards n-butylamine in anhydrous acetonitrile [J].
Cassol, A ;
DiBernardo, P ;
Portanova, R ;
Tolazzi, M ;
Zanonato, PL .
INORGANICA CHIMICA ACTA, 1997, 262 (01) :1-8