Synthesis and Structural Analysis of Novel Phosphonium Hexatungstate Complexes


Sodium tungstate reacted with tetramethyl- and tetrabutyl-phosphonium bromide in presence of hydrochloric acid to afford two new phosphonium hexatungstate compounds ((CH3)4P)2W6O19, 1, and ((CH3CH2CH2CH2)4P)2W6O19, 2, respectively. Under similar conditions, sodium tungstate reacted with methyltriphenyl-, allyltriphenyl-, butyltriphenyl- and benzyltriphenyl-phosphonium bromides to yield four new phosphonium hexatungstate compounds (CH3Ph3P)2W6O19, 3, (CH2CHCH2Ph3P)2W6O19, 4, (CH3CH2CH2CH2Ph3P)2W6O19, 5, and (C6H5CH2Ph3P)2W6O19, 6, respectively. All six compounds appeared to be stable in air, and were structurally characterized by a combination of FTIR, elemental analyses, and single-crystal X-ray diffraction analyses. The steric effect of the phosphonium cation was investigated and found to cause no significant change on the average bond distances of the hexatungstate anion. The crystal structure analyses of these compounds showed that hexatungstate anions were isolated and the distance between the anions increases with increase in the bulkiness of the surrounding phosphonium cations. Moreover, thermal stability and heat absorption of all six compounds were evaluated using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC).

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This material is based upon the work supported by the National Science Foundation and Center for Sustainable Materials Chemistry under Grant No. CHE-1102637.

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Correspondence to Sumit Saha or Douglas A. Keszler.

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Crystallographic data for the structural analysis have been deposited with the Cambridge Crystallographic Data Centre, CCDC Nos. 1439506-1439511 for compounds 16. Copies of this information may be obtained free of charge from, The Director, CCDC 12 Union Road, Cambridge CB2 1EZ, UK [fax: (int.code) +44(1223) 336-033 or e-mail: or].

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Saha, S., Zakharov, L.N., Captain, B. et al. Synthesis and Structural Analysis of Novel Phosphonium Hexatungstate Complexes. J Clust Sci (2020).

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  • Polyoxometalate complex
  • Inorganic cluster
  • X-ray diffraction
  • Phosphonium bromide
  • Sodium tungstate