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Cation‐Anion Interactions and Synergistic Catalysis by Supramolecular Polyoxometalate Complexes [C 10 H 18 N] n [XM 12 O 40 ]
Author(s) -
Cao Jie,
Xu Chong,
Liu Chang,
Liu WeiQi
Publication year - 2016
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201600325
Subject(s) - polyoxometalate , catalysis , chemistry , hydrogen peroxide , supramolecular chemistry , medicinal chemistry , hydrogen bond , crystallography , aqueous solution , counterion , inorganic chemistry , ion , crystal structure , molecule , organic chemistry
A series of novel organic ammonium salts of Keggin [XM 12 O 40 ] n− (X=P, Si, B; M=W, Mo) was synthesized and fully characterized using ESI‐MS and X‐ray crystallography. The solid‐state structure of the title compounds [C 10 H 18 N] n [XM 12 O 40 ] was unveiled by X‐ray crystallography that hydrogen bonds are formed between the nitrogen center of amantadine and the bridging oxygen atoms of POM in addition to Coulombic attractions and by MS/MS that consecutive proton‐transfer reactions from [C 10 H 18 N] + to [XM 12 O 40 ] n− were observed in the gas‐phase fragmentations of the dimeric clusters {(C 10 H 18 N) m [XM 12 O 40 ] 2 } (2n−m)− . A comparative study on the catalytic property of [XM 12 O 40 ] n− in methyl phenyl sulfide (MPS) oxidation with aqueous hydrogen peroxide in MeCN was performed and the effect of counterions ([C 10 H 18 N] + and TBA + , etc) on the catalytic performance has been investigated. The best catalytic activity of [C 10 H 18 N] 3 [PMo 12 O 40 ] in MPS oxidation illustrates the explicit role of cations on promoting catalytic activity of polyoxoanions.