ISSN:
0009-2940
Keywords:
μ-Oxobis(phthalocyaninato)iron
;
μ-Oxo dimers
;
Mössbauer spectroscopy
;
Iron complexes
;
Phthalocyanines
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Attempts to prepare various peripheral tetra- and octasubstituted (phthalocyaninato)iron derivatives RnPcFe [n = 4: R = CH2OEt (6e), CO2Et (6h), CO2-n-C6H13 (6l), O(2-Et-n-C6H13) (6j), OCH2C(CH3)3 (6k), OCH2C(CH3)2CH2Ph (6l); n = 8: R = CH2CH(CO2Me)CH(CO2Me)CH2 (6f), CH2CH(CO2Et)-CH(CO2Et)CH2 (6g), O-n-C8H17 (6m), O(2-Et-n-C6H13) (6n)] by starting from the corresponding substituted phthalonitriles led to substituted (μ-oxo)bis[(phthalocyaninato)iron(III)] compounds [RnPcFe]2O. The tert-butyl- and ethyl-substituted systems [tBu4PcFe]2O (6c) and [Et4PcFe]2O (6d) were reinve-stigated. UV/Vis, FD mass, Mössbauer, NMR as well as ESR spectroscopy was used to characterize the complexes [RnPcFe]2O to furnish evidence for the presence of Fe-O-Fe moieties in [RnPcFe]2O. The UV/Vis data reported for [RnPcFe]2O as well as their spectral behavior in pyridine correspond to unsubstituted [PcFe]2O. Mössbauer spectra of [RnPcFe]2O show that the complexes were obtained as a mixture of two isomeric μ-oxo compounds A (δFe = 0.22 mm s-1, ΔEQ = 1.33-1.39 mm s-1) and B (ΔFe = 0.33-0.36 mm s-1, ΔEQ = 0.39-0.53 mm s-1), whose Mössbauer parameters are comparable to [PcFe]2O μ-oxo(2) and μ-oxo(1), respectively. Mössbauer spectral data of [RnPcFe]2O indicate high-spin (S = 5/2) FeIII centers. NMR-spectra of [RnPcFe]2O (n = 4: R = tBu, Et, O(2-Et-n-C6H13), OCH2C(CH3)2CH2Ph; n = 8: R = O-n-C8H17, O(2-Et-n-C6H13) give further evidence for μ-oxo bridged structures.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19951280611
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