Isolation of a Nitromethane Anion in the Calix-Shaped Inorganic Cage

A calix-shaped polyoxometalate, [V(12)O(32)](4−) (V12), stabilizes an anion moiety in its central cavity. This molecule-sized container has the potential to control the reactivity of an anion. The highly-reactive cyanate is smoothly trapped by V12 to form [V(12)O(32)(CN)](5−). In the CH(3)NO(2) solu...

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Detalles Bibliográficos
Autores principales: Kikukawa, Yuji, Kitajima, Hiromasa, Kuwajima, Sho, Hayashi, Yoshihito
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2020
Materias:
Article
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7729913/
https://www.ncbi.nlm.nih.gov/pubmed/33271966
http://dx.doi.org/10.3390/molecules25235670
Descripción
Sumario:A calix-shaped polyoxometalate, [V(12)O(32)](4−) (V12), stabilizes an anion moiety in its central cavity. This molecule-sized container has the potential to control the reactivity of an anion. The highly-reactive cyanate is smoothly trapped by V12 to form [V(12)O(32)(CN)](5−). In the CH(3)NO(2) solution, cyanate abstracts protons from CH(3)NO(2), and the resultant CH(2)NO(2)(−) is stabilized in V12 to form [V(12)O(32)(CH(2)NO(2))](5−) (V12(CH(2)NO(2))). A crystallographic analysis revealed the double-bond characteristic short bond distance of 1.248 Å between the carbon and nitrogen atoms in the nitromethane anion in V12. (1)H and (13)C NMR studies showed that the nitromethane anion in V12 must not be exchanged with the nitromethane solvent. Thus, the V12 container restrains the reactivity of anionic species.

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