Electronic structure and redox properties of macrocyclic complexes (M(TAAB))/sup n+/ (M = Ni, Cu)
The SCF-LCAO-MO method is the CNDO approximation has been used in calculating the electronic structure of complexes of nickel and copper with the macro-cyclic ligand TAAB, complexes of nickel and cooper with the macrocyclic ligand TAAB, complexes with the general formula (M(TAAB))/sup n+/ (n = 0.3). From an analysis of the distribution of electron density and populations of the AOs of the central ion in these complexes, it has been established that the process of reduction of nickel compounds is accompanied by an increase in electron density on the carbon atoms of the macrocyclic ligand, whereas in the reduction of (Cu(TAAB))/sup 2 +/ a substantial increase is observed in the populations of the 3d AOs of the central ion, i.e., it is reduced. The difference in behavior of the complexes upon reduction is due to differences in the electronic configuration of the central ion. The structure and orbital composition of the frontier MOs have been analyzed, and it has been shown that in the reduced complexes of nickel (Ni(TAAB)), which have strong nucleophilic properties, not only the central ion may act as a nucleophilic center, but also the carbon atoms of the macrocyclic ligand.
- OSTI ID:
- 6281031
- Journal Information:
- Theor. Exp. Chem. (Engl. Transl.); (United States), Vol. 23:4; Other Information: Translated from Teoret. Eksper. Khimiya; 23: No. 4, 421-428(Jul-Aug 1987)
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
COPPER COMPLEXES
ATOMIC MODELS
NICKEL COMPLEXES
CATALYTIC EFFECTS
CHARGE DISTRIBUTION
CONFIGURATION INTERACTION
EFFECTIVE CHARGE
ELECTRON DENSITY
ELECTRON TRANSFER
ELECTRONIC STRUCTURE
LCAO METHOD
LIGANDS
MOLECULAR ORBITAL METHOD
PLATINUM OXIDES
QUANTUM MECHANICS
REDOX POTENTIAL
REDUCTION
SELF-CONSISTENT FIELD
CHALCOGENIDES
CHEMICAL REACTIONS
COMPLEXES
MATHEMATICAL MODELS
MECHANICS
OXIDES
OXYGEN COMPOUNDS
PLATINUM COMPOUNDS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties
657002 - Theoretical & Mathematical Physics- Classical & Quantum Mechanics