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Titolo:
THERMODYNAMICS OF THE HIGH-SPIN-LOW-SPIN CONVERSION OF NICKEL(II) COMPLEXES WITH TETRAAMINE LIGANDS
Autore:
LAI CY; LIU YL; SHU KL; WANG C; CHUNG CS; LUH H;
Indirizzi:
NATL TSING HUA UNIV,DEPT CHEM HSINCHU 300 TAIWAN NATL TSING HUA UNIV,DEPT CHEM HSINCHU 300 TAIWAN CHUNG CHENG INST TECHNOL,DEPT APPL CHEM TAYUAN 335 TAIWAN
Titolo Testata:
Journal of the Chinese Chemical Society
fascicolo: 3, volume: 43, anno: 1996,
pagine: 247 - 252
SICI:
0009-4536(1996)43:3<247:TOTHCO>2.0.ZU;2-H
Fonte:
ISI
Lingua:
ENG
Soggetto:
TO-YELLOW CONVERSION; COPPER(II) COMPLEXES; REDUCTION BEHAVIOR; MACROCYCLES; ION; OXIDATION;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Science Citation Index Expanded
Citazioni:
22
Recensione:
Indirizzi per estratti:
Citazione:
C.Y. Lai et al., "THERMODYNAMICS OF THE HIGH-SPIN-LOW-SPIN CONVERSION OF NICKEL(II) COMPLEXES WITH TETRAAMINE LIGANDS", Journal of the Chinese Chemical Society, 43(3), 1996, pp. 247-252

Abstract

Six tetraamine ligands, 2,5,8,11-tetraazadodecane, 2,5,9,12-tetraazatridecane, 3,7-dimethyl-3,7-diazanonane-1,9-diamine, 2,6,9,13-tetraazatetradecane, 4,7-dimethyl-4,7-diazadecane-1,10-diamine, 4-methyl-4,7-diazadecane-1,10-diamine, and their nickel(II) complexes have been synthesized. The equilibrium constants and thermodynamic parameters of the high-spin-low-spin conversion of these complexes at various temperatures in 0.10 M NaClO4 have been investigated by spectrophotometric techniques. Influences of the enthalpies of these reactions are attributed to an endothermic contribution due to the breaking of the two Ni-OH2 bonds, an exothermic contribution due to the strengthening of the four in-plane Ni-N bonds, an exothermic contribution due to the different ligand field stabilization energies of the square-planar and the octahedral complexes, an endothermic contribution due to the steric repulsions between the N-methyl group(s) and methylene groups as well as that between the two N-methyl groups of the tetraamine, an exothermic contribution due to the steric repulsions between the N-methyl group(s) andthe coordinated water molecules, and an exothermic contribution due to the inductive effect of the N-methyl group(s). The important factorsinfluencing the values of the entropies of these reactions are a negative term due to the reduction of spin multiplicity and a large positive term due to the release or the mobilization of the two coordinated water molecules.

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Documento generato il 20/09/20 alle ore 23:23:31