Deoxygenation of Polynuclear Metal-Oxo Anions: Synthesis, Structure, and Reactivity of the Condensed Polyoxoanion [C4H9]4(NbW5O18) 2O

Ying Jie Lu, Roger Lalancette, Robert H. Beer

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Abstract

The deoxygenation of the mixed-metal polyoxoanion [(C4H9)4N]3NbW5O 19 with benzoyl chloride in dichloromethane forms quantitatively the condensed polyoxanion [(C4H9)4N]4(NbW5O 18)2O, in which two polyoxoanion fragments are linked together by a Nb-O-Nb oxo bridge. The product is characterized by a strong IR band at 692 cm-1 assigned to a Nb-O-Nb stretch and a broad single 93Nb NMR resonance at 975 ppm. Partial hydrolysis of [(C4H9)4N]4(NbW5O 18)2O to NbW5O19O3- in wet acetonitrile was observed by IR and 17O NMR spectroscopy. The reaction of [(C4H9)4N]4(NbW5O 18)2O with a variety of alcohols and phenol forms alkoxide-derivatized polyoxoanions [(C4H9)4N]2Nb(OR)W5O 18 (R = methyl, ethyl, isopropyl, cholesteryl, phenyl). The similarity of the IR spectra of these deriviatives suggests that functionalization occurs at the terminal NbO oxygen. A crystallographic study of [(C4H9)4N]4(NbW5O 18)2O revealed a crystallographically imposed linear Nb-O-Nb oxo bridge (Nb-Obridge = 1.887(3) Å) and a structure in which the terminal tungsten-oxo bonds on the adjoining polyoxoanion fragments are eclipsed. Crystal data: orthorhombic, Cmca; Z = 4, a = 15.817(2) Å, b = 17.870(2) Å, c = 35.058(2) Å; V = 9928.0(10) Å3; R = 5.52%.

Original languageEnglish (US)
Pages (from-to)2524-2529
Number of pages6
JournalInorganic Chemistry
Volume35
Issue number9
DOIs
StatePublished - 1996

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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