Octachloro- And Octabromoditechnetate(III) And Their Rhenium(III) Congeners

The compound (n-Bu{sub 4}N){sub 2}Tc{sub 2}Br{sub 8} was prepared by the metathesis of (n-Bu{sub 4}N){sub 2}Tc{sub 2}Cl{sub 8} with HBr (g) in dichloromethane and characterized by X-ray absorption fine structure spectroscopy and UV-vis spectroscopy. Analysis of the data gives a Tc-Tc distance of 2.1...

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Bibliographic Details
Published in:Inorganic chemistry 2009-05, Vol.47 (6)
Main Authors: Poineau, F., Sattelberger, A.P., Conradson, S.D., Czerwinski, K.R.
Format: Article
Language:English
Subjects:
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
Other,OTHER, CHEM
RHENIUM BROMIDES
RHENIUM CHLORIDES
SPECTROSCOPY
TECHNETIUM BROMIDES
TECHNETIUM CHLORIDES
VALENCE
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Summary:The compound (n-Bu{sub 4}N){sub 2}Tc{sub 2}Br{sub 8} was prepared by the metathesis of (n-Bu{sub 4}N){sub 2}Tc{sub 2}Cl{sub 8} with HBr (g) in dichloromethane and characterized by X-ray absorption fine structure spectroscopy and UV-vis spectroscopy. Analysis of the data gives a Tc-Tc distance of 2.16(1) {angstrom} and a Tc-Br distance of 2.48(1) {angstrom}. The Tc(III) oxidation state was inferred by the position of the edge absorption, which reveals a shift of 12 eV between (n-Bu{sub 4}N){sub 2}Tc{sub 2}Br{sub 8} and NH{sub 4}TcO{sub 4}. The analogous shift between (n-Bu{sub 4}N){sub 2}Tc{sub 2}Cl{sub 8} and NH{sub 4}TcO{sub 4} is 11 eV. The UV-vis spectrum of Tc{sub 2}Br{sub 8}{sup 2-} in dichloromethane exhibits the characteristic {delta} {yields} {delta}* transition at 13717 cm{sup -1}. The M{sub 2}X{sub 8}{sup 2-} (M = Re, Tc; X = Cl, Br) UV-vis spectra are compared, and the position of the {delta} {yields} {delta}* transition discussed.
ISSN:0020-1669
1520-510X