The solution chemistry and reactivity of lacunary Keggin silicotungstates monitored in real-time by a combination of mass spectrometry and electrochemistry

被引：14

作者：

Jia, Qiaodi ^{[1
]}

Cao, Jie ^{[1
]}

Duan, Yunpeng ^{[1
]}

Hu, Changwen ^{[1
]}

机构：

[1] Beijing Inst Technol, Key Lab Cluster Sci, Beijing Key Lab Photoelect Electrophoton Convers, Minist Educ China,Sch Chem, Beijing 100081, Peoples R China

来源：

DALTON TRANSACTIONS | 2015年 / 44卷 / 02期

基金：

中国国家自然科学基金;

关键词：

BUILDING-BLOCKS; POLYOXOTUNGSTATES; PROTONATION; STABILITY; COMPLEXES; CLUSTER; ANIONS;

D O I：

10.1039/c4dt02723j

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The solution chemistry of a series of mono-, di- and trilacunary Keggin silicotungstates was investigated by electrospray ionization mass spectrometry (ESI-MS) and general electrospray features especially for lacunary POMs are summarized. The reactions of vanadium incorporation into the lacunary structures were successfully monitored in real-time by a combination of ESI-MS and differential pulse voltammetry (DPV). It was found that all the reactions took place instantaneously and that a subtle speciation change occurred at prolonged reaction times for the pair of reactants, monovacant silicotungstate and sodium metavanadate, suggesting a conversion of mono- to divanadium substituted derivatives. This was shown to result from a solution process, not an ESI-induced reaction, by DPV measurements. The relative stabilities of the V-substituted products were assessed in both solution and gas phases.

引用

页码：553 / 559

页数：7

共 33 条

[1] Recent Advances in Lanthanide-Containing Polyoxotungstates [J].

Bassil, Bassem S. ;

Kortz, Ulrich .

ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE, 2010, 636 (12) :2222-2231

[2] Formation of unsymmetrical polyoxotungstates via transfer of polyoxometalate building blocks.: NMR evidence supports the kinetic stability of the pentatungstate anion, [W5O18]6-, in aqueous solution [J].

Belai, N ;

Sadakane, M ;

Pope, MT .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (09) :2087-2088

[3] Electrospray behavior of lacunary Keggin-type polyoxotungstates [XW11O39]p- (X = Si, P):: Mass spectrometric evidence for a concentration-dependent incorporation of an MOn+ (M = WVI, MoVI, VV) unit into the polyoxometalate vacancy [J].

Bonchio, M ;

Bortolini, O ;

Conte, V ;

Sartorel, A .

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2003, (04) :699-704

[4] Electrospray ionization mass spectrometry of a cerium(III) phosphomolybdate complex: Condensed and gas-phase cluster chemistry [J].

Bray, Travis H. ;

Copping, Roy ;

Shuh, David K. ;

Gibson, John K. .

INTERNATIONAL JOURNAL OF MASS SPECTROMETRY, 2011, 299 (01) :35-46

[5] Selective Production of Electrostatically-Bound Adducts of Alkyl Cations/Polyoxoanions by the Collision-Induced Fragmentations of Their Quaternary Ammonium Counterparts [J].

Cao, Jie ;

Xu, Chong ;

Fan, YanXuan ;

Fan, LinYuan ;

Zhang, XiuHui ;

Hu, ChangWen .

JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY, 2013, 24 (06) :884-894

[6] Intriguing Role of a Quaternary Ammonium Cation in the Dissociation Chemistry of Keggin Polyoxometalate Anions [J].

Cao, Jie ;

Li, Chenchen ;

Zhang, Zhengxiang ;

Xu, Chong ;

Yan, Jie ;

Cui, Fengyun ;

Hu, Changwen .

JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY, 2012, 23 (02) :366-374

[7] STABILIZATION OF THE DEFECT (LACUNARY) COMPLEX PMO11O39(7-) - ISOLATION, PURIFICATION, STABILITY CHARACTERISTICS, AND METALATION CHEMISTRY [J].

COMBSWALKER, LA ;

HILL, CL .

INORGANIC CHEMISTRY, 1991, 30 (21) :4016-4026

[8] Functionalization of polyoxometalates:: From Lindqvist to Keggin derivatives.: 1.: Synthesis, solution studies, and spectroscopic and ESI mass spectrometry characterization of the rhenium phenylimido tungstophosphate [PW11O39{ReNC6H5}]4- [J].

Dablemont, C ;

Proust, A ;

Thouvenot, R ;

Afonso, C ;

Fournier, F ;

Tabet, JC .

INORGANIC CHEMISTRY, 2004, 43 (11) :3514-3520

[9] Threshold dissociation energies of protonated amine/polyether complexes in a quadrupole ion trap [J].

David, WM ;

Brodbelt, JS .

JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY, 2003, 14 (04) :383-392

[10] Structural, electrochemical, and spectroscopic characterization of a redox pair of sulfite-based polyoxotungstates:: α-[W18O54(SO3)2]4- and α-[W18O54(SO3)2]5- [J].

Fay, Nigel ;

Bond, Alan M. ;

Baffert, Carole ;

Boas, John F. ;

Pilbrow, John R. ;

Long, De-Liang ;

Cronin, Leroy .

INORGANIC CHEMISTRY, 2007, 46 (09) :3502-3510

← 1 2 3 4 →