ISSN:
0947-6539
Schlagwort(e):
cyclovoltammetry
;
electronic effects
;
photoelectron spectroscopy
;
pyrazole ligands
;
Mössbauer spectroscopy
;
Chemistry
;
General Chemistry
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
Notizen:
The electronic effect of substituting CH with N in poly(pyrazolyl)-borato ligands and their transition-metal complexes is shown to be a decrease in energy of the filled metal and ligand orbitals. This conclusion is based on the cyclovoltammograms and photoelectron spectra of bis(hydrotris(azolyl)borato)-iron(II) and -cobalt(II) complexes (azolyl = pyrazolyl and 1,2,4-triazolyl) and on MO calculations. 57Fe Mössbauer spectra of bis(hydrotris(1,2,4-triazolyl)-borato)iron(II) show that there is a fine-tuning of the HOMO-LUMO gap by a shift in transition temperature for the spin equilibrium. 15N NMR spectroscopy supports the assignment of a higher negative charge to the exodentate N-4 nitrogen than to the endodentate N-2 or N-3 positions in the poly(azolyl)borato anions, where azolyl is 1,2,4-triazolyl or tetrazolyl. The electron withdrawing effect of the additional nitrogen atoms and the in-corporation of water of crystallization by O-H ⃛ N bonding both assist in the formation of (azolyl)C-H ⃛ O bonds.
Zusätzliches Material:
6 Ill.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1002/chem.1460020813
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