Premium
Following the Reaction of Heteroanions inside a {W 18 O 56 } Polyoxometalate Nanocage by NMR Spectroscopy and Mass Spectrometry
Author(s) -
Zheng Qi,
VilàNadal Laia,
Busche Christoph,
Mathieson Jennifer S.,
Long DeLiang,
Cronin Leroy
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201502295
Subject(s) - polyoxometalate , chemistry , moiety , mass spectrometry , crystallography , cluster (spacecraft) , nuclear magnetic resonance spectroscopy , reactivity (psychology) , oxidation state , nanocages , spectroscopy , stereochemistry , metal , organic chemistry , catalysis , medicine , physics , alternative medicine , chromatography , pathology , quantum mechanics , computer science , programming language
By incorporating phosphorus(III)‐based anions into a polyoxometalate cage, a new type of tungsten‐based unconventional Dawson‐like cluster, [W 18 O 56 (HP III O 3 ) 2 (H 2 O) 2 ] 8− , was isolated, in which the reaction of the two phosphite anions [HPO 3 ] 2− within the {W 18 O 56 } cage could be followed spectroscopically. As well as full X‐ray crystallographic analysis, we studied the reactivity of the cluster using both solution‐state NMR spectroscopy and mass spectrometry. These techniques show that the cluster undergoes a structural rearrangement in solution whereby the {HPO 3 } moieties dimerize to form a weakly interacting (O 3 PH⋅⋅⋅HPO 3 ) moiety. In the crystalline state the cluster exhibits a thermally triggered oxidation of the two P III template moieties to form P V centers (phosphite to phosphate), commensurate with the transformation of the cage into a Wells–Dawson {W 18 O 54 } cluster.