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Organoarsonate Functionalization of Heteropolyoxotungstates
[Image: see text] Functionalization of the {P(8)W(48)} polyoxotungstate (POT) archetype with aromatic organoarsonates results in the first homometallic {P(8)W(48)} derivatives, with the general formula [(RAs(V)O)(4)P(V)(8)W(VI)(48)O(184)](32−) [R = C(6)H(5) (1) or p-(H(2)N)C(6)H(4) (2)]. Short As−O...
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2017
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5698878/ https://www.ncbi.nlm.nih.gov/pubmed/29120168 http://dx.doi.org/10.1021/acs.inorgchem.7b01928 |
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author | Yi, Xiaofeng Izarova, Natalya V. Kögerler, Paul |
author_facet | Yi, Xiaofeng Izarova, Natalya V. Kögerler, Paul |
author_sort | Yi, Xiaofeng |
collection | PubMed |
description | [Image: see text] Functionalization of the {P(8)W(48)} polyoxotungstate (POT) archetype with aromatic organoarsonates results in the first homometallic {P(8)W(48)} derivatives, with the general formula [(RAs(V)O)(4)P(V)(8)W(VI)(48)O(184)](32−) [R = C(6)H(5) (1) or p-(H(2)N)C(6)H(4) (2)]. Short As−O bonds here induce unusual bending of the otherwise rigid {P(8)W(48)} macrocycle, breaking its D(4h) symmetry. The obtained species also represent the first lacunary POTs functionalized with organoarsonates and can potentially act as polyoxometalate precursors themselves. We elaborate solution stability in different aqueous media using (1)H and (31)P NMR spectroscopy and possible pathways for subsequent transformations in aqueous solutions of the functionalized polyanions. Recrystallization of the K(+)/Li(+)/dimethylammonium salt of 2 from 4 M LiCl solution yielded a further functionalized POT, [(H(3)NC(6)H(4)AsO)(3)P(8)W(48)O(184)H(x){WO(2)(H(2)O)(2)}(0.4)]((30.2−x)−) (3), revealing dissociation of the organoarsonate fragments in slightly acidic aqueous solutions followed by their rearrangement within the inner POT cavity. |
format | Online Article Text |
id | pubmed-5698878 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2017 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-56988782017-11-27 Organoarsonate Functionalization of Heteropolyoxotungstates Yi, Xiaofeng Izarova, Natalya V. Kögerler, Paul Inorg Chem [Image: see text] Functionalization of the {P(8)W(48)} polyoxotungstate (POT) archetype with aromatic organoarsonates results in the first homometallic {P(8)W(48)} derivatives, with the general formula [(RAs(V)O)(4)P(V)(8)W(VI)(48)O(184)](32−) [R = C(6)H(5) (1) or p-(H(2)N)C(6)H(4) (2)]. Short As−O bonds here induce unusual bending of the otherwise rigid {P(8)W(48)} macrocycle, breaking its D(4h) symmetry. The obtained species also represent the first lacunary POTs functionalized with organoarsonates and can potentially act as polyoxometalate precursors themselves. We elaborate solution stability in different aqueous media using (1)H and (31)P NMR spectroscopy and possible pathways for subsequent transformations in aqueous solutions of the functionalized polyanions. Recrystallization of the K(+)/Li(+)/dimethylammonium salt of 2 from 4 M LiCl solution yielded a further functionalized POT, [(H(3)NC(6)H(4)AsO)(3)P(8)W(48)O(184)H(x){WO(2)(H(2)O)(2)}(0.4)]((30.2−x)−) (3), revealing dissociation of the organoarsonate fragments in slightly acidic aqueous solutions followed by their rearrangement within the inner POT cavity. American Chemical Society 2017-11-09 2017-11-20 /pmc/articles/PMC5698878/ /pubmed/29120168 http://dx.doi.org/10.1021/acs.inorgchem.7b01928 Text en Copyright © 2017 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes. |
spellingShingle | Yi, Xiaofeng Izarova, Natalya V. Kögerler, Paul Organoarsonate Functionalization of Heteropolyoxotungstates |
title | Organoarsonate Functionalization of Heteropolyoxotungstates |
title_full | Organoarsonate Functionalization of Heteropolyoxotungstates |
title_fullStr | Organoarsonate Functionalization of Heteropolyoxotungstates |
title_full_unstemmed | Organoarsonate Functionalization of Heteropolyoxotungstates |
title_short | Organoarsonate Functionalization of Heteropolyoxotungstates |
title_sort | organoarsonate functionalization of heteropolyoxotungstates |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5698878/ https://www.ncbi.nlm.nih.gov/pubmed/29120168 http://dx.doi.org/10.1021/acs.inorgchem.7b01928 |
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