ISSN:
0894-3230
Schlagwort(e):
Organic Chemistry
;
Physical Chemistry
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
,
Physik
Notizen:
The octaethyltetrathiaporphyrin dication, OTP2+, forms 1:1 intermolecular donor-acceptor complexes with NiII-, VIVO- and FeIII-octaethylporphyrins. The association constants of the complexes are governed by the oxidation potential of the metallo-octaethylporphyrins and by secondary electrostatic interactions. Octaethylporphyrin, H2OEP, forms intermolecular complexes with OTP2+. Kinetic analyses of the formation of the various complexes revealed the formation of a primary complex exhibiting the stoichiometry (OTP2+)2(H2OEP). This intermolecular complex transforms into a thermodynamically stabilized intermolecular assembly with a stoichiometry corresponding to (OTP2+)4H2OEP. The activation barrier associated with the conversion of the primary complex to the thermodynamically stabilized assembly is Ea = 16·5 kcal mol-1 (1 kcal = 4·184 kJ). The association constant of the complex (OTP2+)2(H2OEP) is K1 = 1·3 × 1010 M-2 and the equilibrium constant between the two coexisting intermolecular complexes (OTP2+)4(H2OEP) and (OTP2+)2(H2OEP) is K2 = 7·4.
Zusätzliches Material:
9 Ill.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1002/poc.610081005
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