Structural and electron self-exchange rate variations in isomeric (hexaamine)cobalt(III/II) complexes
- Univ. of Queensland, Brisbane (Australia)
The synthesis and characterization of the new macrocyclic hexaamine trans-(5(S),12(R), 14(R)-tetramethyl)-1,4,8,11-tetraazacyclotetradecane-6,13-diamine (L{sup 6}) and its Co{sup III} complex are reported. The X-ray crystal structural analyses of [CoL{sup 6}]Cl{sub 2}(ClO{sub 4}) and the closely related cis-diamino-substituted macrocyclic complex [CoL{sup 2}](ClO{sub 4}){sub 3}{center_dot} 2H{sub 2}O reveal significant variations in the observed Co-N bond lengths and coordination geometries, which may be attributed to the trans or cis disposition of the pendent primary amines. The Co{sup III/II} self-exchange electron transfer rate constants for these and other closely related hexaamines have been determined, and variations of some 2 orders of magnitude are found between pairs of trans and cis isomeric Co{sup III} complexes. 30 refs., 5 figs., 3 tabs.
- OSTI ID:
- 563609
- Journal Information:
- Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 11 Vol. 36; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
36 MATERIALS SCIENCE
40 CHEMISTRY
AMINES
BOND ANGLE
BOND LENGTHS
CHEMICAL BONDS
COBALT COMPLEXES
COMPARATIVE EVALUATIONS
CRYSTAL STRUCTURE
ELECTROCHEMISTRY
ELECTRON TRANSFER
ISOMERIZATION
LIGANDS
MOLECULAR STRUCTURE
NMR SPECTRA
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
TENSILE PROPERTIES
VARIATIONS
X-RAY DIFFRACTION
40 CHEMISTRY
AMINES
BOND ANGLE
BOND LENGTHS
CHEMICAL BONDS
COBALT COMPLEXES
COMPARATIVE EVALUATIONS
CRYSTAL STRUCTURE
ELECTROCHEMISTRY
ELECTRON TRANSFER
ISOMERIZATION
LIGANDS
MOLECULAR STRUCTURE
NMR SPECTRA
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
TENSILE PROPERTIES
VARIATIONS
X-RAY DIFFRACTION