Phenyltin-Substituted 9-Tungstogermanate and Comparison with Its Tungstosilicate Analogue
- 4 September 2008
- journal article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 47 (19), 8798-8806
- https://doi.org/10.1021/ic800852d
Abstract
Reaction of (C6H5)SnCl3 with Na10[A-α-GeW9O34] in water results in the monomeric, trisubstituted Keggin species [{(C6H5)Sn(OH)}3(A-α-GeW9O34)]4− (1), constituting the first organotin derivative of a trilacunary Keggin tungstogermanate. Polyanion 1 could be obtained as two different cesium salts depending on the applied isolation strategy: Cs3Na[{(C6H5)Sn(OH)}3(A-α-GeW9O34)]·9H2O (CsNa-1) and Cs3[{(C6H5)Sn(OH)}3(A-α-HGeW9O34)]·8H2O (Cs-H1). The monomeric phenyltin-containing tungstosilicate [{(C6H5)Sn(OH)}3(A-α-SiW9O34)]4− (2) and the dimeric, sandwich-type derivative [{(C6H5)Sn(OH)}3(A-α-H3SiW9O34)2]8− (3) have also been isolated as the cesium salts Cs3Na[{(C6H5)Sn(OH)}3(A-α-SiW9O34)]·9H2O (CsNa-2), Cs4[{(C6H5)Sn(OH)}3(A-α-SiW9O34)]·13H2O (Cs-2), and Cs8[{(C6H5)Sn(OH)}3(A-α-H3SiW9O34)2]·23H2O (Cs-3), respectively. We have investigated in detail the similarities and differences in the reactivity of (C6H5)Sn3+ with [A-α-GeW9O34]10− vs [A-α-SiW9O34]10−. All five compounds have been characterized in the solid state by means of elemental analysis, infrared spectroscopy, thermogravimetry, and single-crystal X-ray diffraction, representing the first structural analysis for polyanions 1−3. A full solution characterization of 1 by multinuclear NMR spectroscopy (1H, 13C, 119Sn, and 183W) has also been performed. The monomeric polyanions 1 and 2 are closely associated in the solid state through (Sn)O−H···Ot (Ot: terminal oxygen atom) hydrogen bonds reinforced by weak C−H···Ot contacts to form 2-dimensional (CsNa-1 and CsNa-2) or 1-dimensional (Cs-H1) arrangements, and also dimeric entities (Cs-2) depending on the network of intermolecular interactions.This publication has 45 references indexed in Scilit:
- Organotin and organogermanium linkers for simple, direct functionalization of polyoxotungstatesElectronic supplementary information (ESI) available: syntheses. See http://www.rsc.org/suppdata/dt/b4/b402421d/Dalton Transactions, 2004
- Polyoxometalate Molecular SciencePublished by Springer Science and Business Media LLC ,2003
- Organotin Derivatives of α-[XIIIW9O33]9- (X = As, Sb) Heteropolytungstates. Solution- and Solid-State Characterization of [{(C6H5Sn)2O}2H(α-AsW9O33)2]9- and [(C6H5Sn)3Na3(α-SbW9O33)2]6-Inorganic Chemistry, 2000
- Polyoxometalate Derivatives with Multiple Organic Groups. 2. Synthesis and Structures of Tris(organotin) α, β-Keggin TungstosilicatesInorganic Chemistry, 1996
- Polyoxometalate Derivatives with Multiple Organic Groups. 3. Synthesis and Structure of Bis(phenyltin) Bis(decatungstosilicate), [(PhSnOH2)2(γ-SiW10O36)2]10-Inorganic Chemistry, 1996
- Polyoxometalate Derivatives with Multiple Organic Groups. 1. Synthesis and Structures of Tris(organotin) .beta.-Keggin and .alpha.-Dawson TungstophosphatesOrganometallics, 1994
- Polyoxometalates: From Platonic Solids to Anti-Retroviral ActivityPublished by Springer Science and Business Media LLC ,1994
- Polyoxometalate Chemistry: An Old Field with New Dimensions in Several DisciplinesAngewandte Chemie, 1991
- Heteropoly and Isopoly OxometalatesPublished by Springer Science and Business Media LLC ,1983
- Attachment of organic groups to heteropoly oxometalate anionsJournal of the American Chemical Society, 1979