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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...

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Autores principales: Yi, Xiaofeng, Izarova, Natalya V., Kögerler, Paul
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2017
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.
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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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