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- W2016089192 abstract "UV-Vis and ESR spectroscopy have been used to study the behaviour of Cs2[TcNCl5] and the hydrolysis product [{TcN(OH)(OH2)}2(μ-O)2] (1) in concentrated and aqueous solutions of a variety of sulfur and phosphorus oxo acids ranging from the very weakly coordinating CF3SO3H to H2SO4 and the coordinating acids H3PO4 and H4P2O7. The paramagnetic monomeric TcVIN3− (d1) forms were readily identified by ESR spectroscopy and the diamagnetic dimeric μ-oxo (Tc2N2O4+) and di(μ-oxo) (Tc2N2O22+) forms by their UV-Vis spectra. For solutions of Cs2[TcNCl5] the chemical form of TcVIN and the rate of the conversion of monomer→μ-oxo dimer→di(μ- oxo) dimer is dependent on the presence of Cl− and the concentration and complexing ability of the acid, with the monomeric form being favoured by the acids of greater complexing power. For solutions of 1 the reverse order of conversion was observed. In 1 M CF3SO3H, MeSO3H or toluene-p-sulfonic acid, 1 is converted to the di(μ-oxo) aquanitrido cation [{TcN(OH2)3}2(μ-O)2]2+ while in 7.5 M CF3SO3H it is proposed that the predominant form is the μ-oxo aqua dimer [{TcN(OH2)4}2(μ-O)]4+. In H2SO4 and the phosphorus oxo acids the aqua cations are coordinated by the acid anions. The monomeric aqua cation, [TcN(OH2)5]3+, does not appear to be a viable species, as is also the case for MoO3+(aq), and spontaneously dimerises in 7.5 M CF3SO3H. In anhydrous CF3SO3H or H2SO4 monomeric TcVIN with CF3SO3− or HSO4− coordination is observed. A characteristic feature of the UV-Vis spectra of monomeric TcVIN is a strong absorption at 266–300 nm assigned to πN→Tc charge transfer. The μ-oxo dimers show an intense visible absorption at 470–510 nm." @default.
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- W2016089192 date "1993-02-01" @default.
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- W2016089192 title "A spectrophotometric and ESR study of monomer, μ-oxo dimer, di(μ-oxo) dimer interconversion of nitridotechnetium(VI) complexes in solutions of sulfur and phosphorus oxo acids" @default.
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