Alkali-metal ion coordination in uranyl(VI) poly-peroxo complexes in solution, inorganic analogues to crown-ethers. Part 2. Complex formation in the tetramethyl ammonium-, Li(+)-, Na(+)- and K(+)-uranyl(VI)-peroxide-carbonate systems

Dalton Transactions : an International Journal of Inorganic Chemistry
Pier Luigi ZanonatoIngmar Grenthe

Abstract

The constitution and equilibrium constants of ternary uranyl(vi) peroxide carbonate complexes [(UO2)p(O2)q(CO3)r](2(p-q-r)) have been determined at 0 °C in 0.50 M MNO3, M = Li, K, and TMA (tetramethyl ammonium), ionic media using potentiometric and spectrophotometric data; (17)O NMR data were used to determine the number of complexes present. The formation of cyclic oligomers, "[(UO2)(O2)(CO3)]n", n = 4, 5, 6, with different stoichiometries depending on the ionic medium used, suggests that Li(+), Na(+), K(+) and TMA ions act as templates for the formation of uranyl peroxide rings where the uranyl-units are linked by μ-η(2)-η(2) bridged peroxide-ions. The templating effect is due to the coordination of the M(+)-ions to the uranyl oxygen atoms, where the coordination of Li(+) results in the formation of Li[(UO2)(O2)(CO3)]4(7-), Na(+) and K(+) in the formation of Na/K[(UO2)(O2)(CO3)]5(9-) complexes, while the large tetramethyl ammonium ion promotes the formation of two oligomers, TMA[(UO2)(O2)(CO3)]5(9-) and TMA[(UO2)(O2)(CO3)]6(11-). The NMR spectra demonstrate that the coordination of Na(+) in the five- and six-membered oligomers is significantly stronger than that of TMA(+); these observations suggest that the templating effect...Continue Reading

References

Feb 20, 2002·Chemical Reviews·Achim MüllerDante Gatteschi
Oct 28, 2009·Inorganic Chemistry·Ginger E SigmonPeter C Burns
Nov 19, 2009·Journal of the American Chemical Society·Ginger E SigmonPeter C Burns
Feb 5, 2010·Angewandte Chemie·De-Liang LongLeroy Cronin
Oct 5, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Pier Luigi ZanonatoIngmar Grenthe
Jun 15, 2012·Chemical Society Reviews·May Nyman, Peter C Burns
Aug 4, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Pier Luigi ZanonatoIngmar Grenthe
Oct 26, 2012·Chemical Reviews·Jie Qiu, Peter C Burns
Dec 5, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Pier Luigi ZanonatoIngmar Grenthe
Mar 19, 2014·Journal of the American Chemical Society·Brendan T McGrailPeter C Burns

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Citations

Aug 20, 2016·Chemistry : a European Journal·Clément Falaise, May Nyman
Oct 3, 2020·Chemical Communications : Chem Comm·Jerome KretzschmarThorsten Stumpf

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