Solution chemistry and electronic structure of binuclear manganese complexes
The electronic structure and solution chemistry of the mixed valence manganese complexes ((L)/sub 2/MnO)/sub 2/(ClO/sub 4/)/sub 3/ where L = 2,2'-bipyridine or 1,10-phenanthroline have been examined. Examination of the optical spectra of the mixed valent (III, IV) complexes with L = 2,2'-bipyridine and 1,10-phenanthroline has demonstrated the presence of a broad near infrared band which is unexpected from comparison with other high spin Mn(III) complexes. Far infrared bands have been tentatively assigned for Mn(III)-N and Mn(IV)-N stretches. One vibrational mode of the Mn/sub 2/O/sub 2/ bridge (for the bipyridyl (III, IV) dimer) has been identified at 688 cm/sup -1/ by /sup 18/O isotopic substitution; analogous bands are found for the phenanthroline (III, IV) and (IV, IV) ions, verifying di-oxo bridged structures for these complexes. Cyclic voltammograms of the bipyridyl and phenanthroline (III, IV) dimers have shown the (III, IV) to (IV, IV) oxidation to occur in a quasi-reversible process at 1.3 V vs. SCE. These oxidations have been established to be one electron processes by controlled potential coulometry. In addition, reductions to the (III, III) ions have been observed, but only in the case of the phenanthroline (III, III) dimer does any measurable current occur for the reoxidation of (III, III) to (III, IV).
- Research Organization:
- California Univ., Berkeley (USA). Lawrence Berkeley Lab.
- DOE Contract Number:
- W-7405-ENG-48
- OSTI ID:
- 7131570
- Report Number(s):
- LBL-5513
- Resource Relation:
- Other Information: Thesis
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
MANGANESE COMPLEXES
ELECTRONIC STRUCTURE
INFRARED SPECTRA
PHENANTHROLINES
PYRIDINES
VALENCE
AZINES
COMPLEXES
HETEROCYCLIC COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
SPECTRA
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)