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...

Descripción completa

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
_version_ 1783621566264770560
author Kikukawa, Yuji
Kitajima, Hiromasa
Kuwajima, Sho
Hayashi, Yoshihito
author_facet Kikukawa, Yuji
Kitajima, Hiromasa
Kuwajima, Sho
Hayashi, Yoshihito
author_sort Kikukawa, Yuji
collection PubMed
description 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.
format Online
Article
Text
id pubmed-7729913
institution National Center for Biotechnology Information
language English
publishDate 2020
publisher MDPI
record_format MEDLINE/PubMed
spelling pubmed-77299132020-12-12 Isolation of a Nitromethane Anion in the Calix-Shaped Inorganic Cage Kikukawa, Yuji Kitajima, Hiromasa Kuwajima, Sho Hayashi, Yoshihito Molecules Article 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. MDPI 2020-12-01 /pmc/articles/PMC7729913/ /pubmed/33271966 http://dx.doi.org/10.3390/molecules25235670 Text en © 2020 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Kikukawa, Yuji
Kitajima, Hiromasa
Kuwajima, Sho
Hayashi, Yoshihito
Isolation of a Nitromethane Anion in the Calix-Shaped Inorganic Cage
title Isolation of a Nitromethane Anion in the Calix-Shaped Inorganic Cage
title_full Isolation of a Nitromethane Anion in the Calix-Shaped Inorganic Cage
title_fullStr Isolation of a Nitromethane Anion in the Calix-Shaped Inorganic Cage
title_full_unstemmed Isolation of a Nitromethane Anion in the Calix-Shaped Inorganic Cage
title_short Isolation of a Nitromethane Anion in the Calix-Shaped Inorganic Cage
title_sort isolation of a nitromethane anion in the calix-shaped inorganic cage
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7729913/
https://www.ncbi.nlm.nih.gov/pubmed/33271966
http://dx.doi.org/10.3390/molecules25235670
work_keys_str_mv AT kikukawayuji isolationofanitromethaneanioninthecalixshapedinorganiccage
AT kitajimahiromasa isolationofanitromethaneanioninthecalixshapedinorganiccage
AT kuwajimasho isolationofanitromethaneanioninthecalixshapedinorganiccage
AT hayashiyoshihito isolationofanitromethaneanioninthecalixshapedinorganiccage

Ejemplares similares