The characterization of a new heteropolytungstoarsonate anion, [CH3AsW7O27H]7-. Topological relationships among ions related to the Lindqvist structure

Jameson, Geoffrey B.; Pope, Michael T.; Wasfi, Sadiq H.

doi:10.1021/ja00303a016

Cited by 15 publications

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“…The anions [(RAs)W 7 O 27 H] 7- , which are formed in solutions of WO 4 2- and RAsO 3 2- at pH 7−8.5, have an unusual stoichiometry . An X-ray crystal structure analysis of (CN 3 H 6 ) 7 [(MeAs)W 7 O 27 H]·3H 2 O has been performed.…”

Section: Organophosphonate and Organoarsonate Ligandsmentioning

confidence: 99%

“…The anion is composed of a {W 7 O 24 } group topologically related to the paratungstate-A structure, and a MeAsO 3 moiety which sits above one or the other of two chemically distinct triangles of edge-sharing octahedra (Figure ). The relationships among the species [W 7 O 24 ] 6- , [(RAs)W 7 O 27 H] 7- , and [(RAs) 2 W 6 O 25 H] 5- have been discussed . An AsMo 7 species with a different overall stoichiometry, [(PhAs)Mo 7 O 25 ] 4- , has been obtained from the reaction of ( n -Bu 4 N) 4 [α-Mo 8 O 26 ] with ( n -Bu 4 N) 4 [(PhAs) 2 Mo 6 O 24 ] in acetonitrile …”

Section: Organophosphonate and Organoarsonate Ligandsmentioning

confidence: 99%

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Main-Group Element, Organic, and Organometallic Derivatives of Polyoxometalates

1998

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ContentsI. Introduction 77 II. Scope and Organization of the Review 78 III. Polyoxometalates Incorporating Halides 79 IV. Polyoxometalates Incorporating Group 16 Element-Centered Ligands 81 A. Peroxopolyoxometalates 81 B. Polyoxoalkoxometalates 82 1. Polyoxoalkoxometalates Involving Unidentate Alcohols 82 2. Polyoxoalkoxometalates Involving Chelating Triols 83 C. Heavier Group 16 Element-Centered Ligands 85 1. Thiopolyoxometalates 85 2. Organosulfur and Organoselenium Ligands 85 V. Polyoxometalates Incorporating Group 15 Element-Centered Ligands 86 A. Singly Bonded Nitrogen-Donating Ligands 86 1. Amine and Related Ligands 86 2. Amide Oximes [RC(NH 2 )NOH] and Oximes 87 B. Multiply Bonded Nitrogen Ligands 89 1. Nitrido Derivatives 89 2. Organoimido Derivatives 89 3. Hydrazido and Diazenido Derivatives of Polyoxometalates 90 4. Nitrosyl Derivatives 92 C. Organophosphorus, Organoarsenic, and Organoantimony Ligands 94 1. Organophosphonate and Organoarsonate Ligands 94 2. Organophosphinate and Organoarsinate Ligands 97 VI. Polyoxometalates Incorporating Group 14 Element-Centered Ligands 97 A. Oxocarbon Ligands 97 1. Carbonate 97 2. Carboxylates 97 3. Oxalate and Squarate 97 4. Carbonyl Derivatives 98 B. Silicon Derivatives 98 C. Germanium Derivatives 99 D. Tin and Lead Derivatives 99 VII. Organometallic Derivatives of Polyoxometalates 100 A. Cyclopentadienyl Derivatives of Polyoxometalates 100 B. Cyclopentadienyl Oxide Clusters of Groups 5 and 6 100 C. Organometallic Polyoxometalates 100 1. Polyoxometalate-incorporated Organometalic Complexes 101 2. Polyoxometalate-Supported Organometallic Complexes 101 3. Integrated Cubane-Type Clusters 105 4. Organometallic Cation Salts of Keggin-Type Anions 105 VIII. Concluding Remarks 106 IX. Acknowledgments 106 X. Abbreviations 106 XI. References 106

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Section: Organophosphonate and Organoarsonate Ligandsmentioning

confidence: 99%

Section: Organophosphonate and Organoarsonate Ligandsmentioning

confidence: 99%

Main-Group Element, Organic, and Organometallic Derivatives of Polyoxometalates

1998

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“…are known, organoarsonate-containing POTs are restricted to the isopolyoxotungstate derivatives [(RAs V O 3 ) 2 W 6 O 18 ] 6− and [(RAs V O 3 )W 7 O 24 H] 7− . 4k,5 These species were obtained by the direct condensation of tungstate ions with organoarsonates in aqueous media (pH 5−8).…”

Section: Introductionmentioning

confidence: 99%

“…While a series of organoarsinates [R 2 As V Mo VI 4 O 15 H] 2− (R = CH 3 , C 2 H 5 , C 6 H 5 ) and organoarsonate-functionalized polyoxomolybdates with formulas [(RAs V O 3 ) 4 Mo VI 4 O 10 ] 4− , , [(RAs V O 3 ) 2 Mo VI 5 O 15 ] 4− , [(MeAs V O 3 )Mo VI 6 O 18 (H 2 O) 6 ] 2− , [(RAs V O 3 ) 2 Mo VI 6 O 18 ] 4− , ,,,, [(RAs V O 3 ) 2 Mo VI 6 O 19 H x ] (6− x )− , ,, [(PhAs V O 3 )Mo VI 7 O 22 ] 4− , and [(RAs V O 3 ) 4 Mo VI 12 O 34 ] 4− , ,− , and several Mo V -based and mixed-valent Mo V/VI species ,, [R = CH 3 , n -C 3 H 7 , C 6 H 5 , C 6 H 4 (CH 3 ), p -C 6 H 4 (NH 2 ), p -C 6 H 4 (OH), p -C 6 H 4 (COOH), p -C 6 H 4 (CN), o -C 6 H 4 (NO 2 ), C 6 H 3 -4-OH-3-NO 2 , C 6 H 3 -4-OH-3-N(H)C(O)CH 3 , etc.] are known, organoarsonate-containing POTs are restricted to the isopolyoxotungstate derivatives [(RAs V O 3 ) 2 W 6 O 18 ] 6− and [(RAs V O 3 )W 7 O 24 H] 7− . , These species were obtained by the direct condensation of tungstate ions with organoarsonates in aqueous media (pH 5−8).…”

Section: Introductionmentioning

confidence: 99%

Organoarsonate Functionalization of Heteropolyoxotungstates

Izarova

Kögerler

2017

Inorg. Chem.

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Functionalization of the {P8W48} polyoxotungstate (POT) archetype with aromatic organoarsonates results in the first homometallic {P8W48} derivatives, with the general formula [(RAsVO)4PV8WVI48O184]32− [R = C6H5 (1) or p-(H2N)C6H4 (2)]. Short As−O bonds here induce unusual bending of the otherwise rigid {P8W48} macrocycle, breaking its D4h 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 1H and 31P 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, [(H3NC6H4AsO)3P8W48O184Hx{WO2(H2O)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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“…However, despite the fact that numerous sandwich-type polyoxoanions have been synthesized, most of the lacunary POM units are limited to one to three lacunary moieties that derived from the well-known classic building units such as Keggin and Dawson-type species. Meanwhile, it is worth noting that sandwich-type polyoxoanions constructing from tetra-or even higher lacunary POM fragments are less reported [36,37], since high lacunary polyoxoanions are always prepared in the comparatively high pH value, however, such condition always leads to totally collapsing of POM frameworks and quick precipitation instead of the formation of new lacunary polyoxoanions or crystalline compounds. On the other hand, the formation mechanism of POMs is still not well understood.…”

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confidence: 99%