ΦΑΣΜΑΤΟΣΚΟΠΙΚΗ ΚΑΙ ΗΛΕΚΤΡΟΧΗΜΙΚΗ ΜΕΛΕΤΗ ΕΝΩΣΕΩΝ ΣΥΝΑΡΜΟΓΗΣ ΤΟΥ ΚΟΒΑΛΤΙΟΥ (ΙΙΙ) ΚΑΙ ΧΑΛΚΟΥ (ΙΙ) ΜΕ Β-ΔΙΟΝΕΣ

THE SPECTRAL AS WELL AS THE ELECTROCHEMICAL STUDY OF THE CO(III) AND CU(II) B-DIONATO CHELATES REVEALED THAT THE INFLUENCE OF THE SUBSTITUENTS IS INDUCTIVE INNATURE. FOR BOTH SERIES IT WAS FOUND THAT THE STRETCHING FREQUENCIES AS WELL AS THE POLAROGRAPHIC REDUCTION POTENTIALS ARE LINEARELY DEPENDENT ON HAMMETT Σ FUNCTIONS. IN THE CASE OF CO(III) CHELATES SIMILARLY DEPENDENT ARE THE RACAH PARAMETER B AND THE ENERGY OF THE FRONTIER MOLECULAR ORBITALS. FURTHERMORE IT WAS ESTABLISHED THAT THE INDUCTIVE EFFECTS MODIFY THE SPHERICAL PORTION OF THE LIGAND FIELD AND THAT THE NEPLELAUXETIC EFFECT MUST BE CONSIDERED AS THE RESULT OF BOTH KINDS OF COVALENT INTERACTIONS. THE FIRST CT BAND IS ASSIGNED TO A P*--T2GEXCITATION. THE EXPERIMENTALLY DETERMINED ENERGIES OF THE HOMO AND LUMO ORBITALS ARE IN EXCELLENT AGREEMENT WITH PREVIOUSLY COMPUTED VALUES. IN ADDITION THESE LOW-SPIN CHELATES UNDERGO A TWO-STEP REDUCTION, THE FIRST ONE BEING MONOELECTRONIC AND PRACTICALLY REVERSIBLE. IN THE CASE OF THE CU(II) CHELATES THE BAND APPEARING AT N 400 MM-1 IS ASSIGNED TO A DXY--ΣL EXCITATION. THE REVERSIBILITY OF THE CATHODIC TRANSFER IS INFLUENCED BY A COMBINATION OF INDUCTIVE AND RESONANCE EFFECTS. ON THE BASIS OF THE MECHANISM THESE CHELATES MAY BE CLASSIFIED INTOTWO SUBGROUPS: THE FIRST ONE COMPRISES COMPOUNDS UNDERGOING A TWO-ELECTRON REDUCTION WHILE THE SECOND ONE CONSISTS OF CHELATES REDUCED IN TWO ONE-ELECTRON STEPS.

Grantor dc:publisher

Aristotle University Of Thessaloniki (AUTH)

Year dc:date

1989

Authors dc:creator

• Cambanis, Stavros
• Καμπάνης, Σταύρος

• CHARGE-TRANSFER BANDS
• FRONTIER MOLECULAR ORBITALS
• HAMMETT-FUNCTIONS
• LIGAND FIELD PARAMETERS
• NEPHELAUXETIC EFFECT
• POLAROGRAPHIC POTENTIALS
• REDUCTION-OXIDATION MECHANISM
• SOLVATED COPPER (I)
• STRETCHING FREQUENCIES
• ΕΝΕΡΓΕΙΑ ΜΕΤΩΠΙΚΩΝΤΡΟΧΙΑΚΩΝ
• ΕΠΙΔΥΑΛΥΤΩΜΕΝΟΣ ΜΟΝΟΣΘΕΝΗΣ ΧΑΛΚΟΣ
• ΜΗΧΑΝΙΣΜΟΙ ΝΕΦΕΛΑΥΞΗΤΙΚΟΥ ΑΠΟΤΕΛΕΣΜΑΤΟΣ
• ΜΗΧΑΝΙΣΜΟΣ ΟΞΕΙΔΟΑΝΑΓΩΓΗΣ
• ΠΑΡΑΜΕΤΡΟΙ HAMMETT
• ΠΑΡΑΜΕΤΡΟΙ ΠΕΔΙΟΥ ΥΠΟΚΑΤΑΣΤΑΤΩΝ
• ΠΟΛΑΡΟΓΡΑΦΙΚΑ ΔΥΝΑΜΙΚΑ
• ΣΥΧΝΟΤΗΤΑ ΔΟΝΗΣΗΣ ΤΑΣΗΣ
• ΤΑΙΝΙΑ ΜΕΤΑΦΟΡΑΣ ΦΟΡΤΙΟΥ
• Φυσικές Επιστήμες
• Χημεία
• Natural Sciences
• Chemical Sciences

Language dc:language

gre

Identifier

10.12681/eadd/1240

OAI identifier oai:identifier

oai:10442/1240