Electronic structure and redox properties of macrocyclic complexes (M(TAAB))/sup n+/ (M = Ni, Cu)

Journal Article · Fri Jan 01 04:00:00 EST 1988 · Theor. Exp. Chem. (Engl. Transl.); (United States)

OSTI ID:6281031

Beletskii, I P

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), Journal Name: Theor. Exp. Chem. (Engl. Transl.); (United States) Vol. 23:4; ISSN TEXCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
657002 -- Theoretical & Mathematical Physics-- Classical & Quantum Mechanics
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
ATOMIC MODELS
CATALYTIC EFFECTS
CHALCOGENIDES
CHARGE DISTRIBUTION
CHEMICAL REACTIONS
COMPLEXES
CONFIGURATION INTERACTION
COPPER COMPLEXES
EFFECTIVE CHARGE
ELECTRON DENSITY
ELECTRON TRANSFER
ELECTRONIC STRUCTURE
LCAO METHOD
LIGANDS
MATHEMATICAL MODELS
MECHANICS
MOLECULAR ORBITAL METHOD
NICKEL COMPLEXES
OXIDES
OXYGEN COMPOUNDS
PLATINUM COMPOUNDS
PLATINUM OXIDES
QUANTUM MECHANICS
REDOX POTENTIAL
REDUCTION
SELF-CONSISTENT FIELD
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS