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

Molecules

Yuji Kikukawa¹  Yoshihito Hayashi¹  Sho Kuwajima¹  Hiromasa Kitajima¹ 

[1] Department of Chemistry, Graduate School of Natural Science and Technology, Kanazawa University Kakuma, Kanazawa 920-1192, Japan;

关键词: calixarene-like structure;    polyoxometalates;    nitronate;    crystal structure;    host–guest chemistry;    anion receptor;   

DOI  :  10.3390/molecules25235670

来源: DOAJ

【 摘 要 】

A calix-shaped polyoxometalate, [V₁₂O₃₂]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 [V₁₂O₃₂(CN)]⁵⁻. In the CH₃NO₂ solution, cyanate abstracts protons from CH₃NO₂, and the resultant CH₂NO₂⁻ is stabilized in V12 to form [V₁₂O₃₂(CH₂NO₂)]⁵⁻ (V12(CH₂NO₂)). 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. ¹H and ¹³C 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.

【 授权许可】

Unknown