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Royal Society of Chemistry, Dalton Transactions, 13, p. 1334

DOI: 10.1039/b617390j

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Synthesis and reactivity of {Ru(p-cymene)}<sup>2+</sup>derivatives of [Nb<sub>6</sub>O<sub>19</sub>]<sup>8−</sup>: a rational approach towards fluxional organometallic derivatives of polyoxometalates

Journal article published in 2007 by Danielle Laurencin, René Thouvenot, Kamal Boubekeur, Anna Proust ORCID
This paper was not found in any repository, but could be made available legally by the author.
This paper was not found in any repository, but could be made available legally by the author.

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Abstract

Three {Ru(p-cym)}2+ (p-cym = p-cymene) derivs. of [Nb6O19]8--[Nb6O19{Ru(p-cym)}]6- (Nb6Ru1), trans-[Nb6O19{Ru(p-cym)}2]4- (t-Nb6Ru2), and [Nb6O19{Ru(p-cym)}4] (Nb6Ru4)-have been synthesized in water by reaction between [Ru(p-cym)Cl2]2 and the hexaniobate. In the solid state, Nb6Ru1 and Nb6Ru4 have been characterized by IR and EDX spectroscopies, whereas t-Nb6Ru2 has been characterized by IR spectroscopy and single-crystal x-ray diffraction (crystal data for K4-trans-[Nb6O19{Ru(p-cym)}2].14H2O (K4-t-Nb6Ru2.14H2O)). In soln., all compds. were characterized by 1H NMR and ESI mass spectrometry analyses, and Nb6Ru1 was also analyzed by 17O NMR. These studies allowed a comparison of the differences in behavior of the three complexes in water: Nb6Ru1 is particularly stable, Nb6Ru4 decomps. by loss of {Ru(p-cym)}2+ fragments, and trans-[Nb6O19{Ru(p-cym)}2]4- isomerizes into cis-[Nb6O19{Ru(p-cym)}2]4-. A rational mechanism for the isomerization of t-Nb6Ru2 is proposed on the basis of a kinetic study.