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DOI: 10.1039/A701381G (Paper) Reference Section for: J. Mater. Chem., 1997, 7, 2053-2061

Chemical routes to oxides: alkoxidevs. alkoxide–acetate routes: synthesis, characterization, reactivity and polycondensation of MNb2(OAc)2(OPri)10(M=Mg, Cd, Pb) species

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Souad Boulmaâz, Renée Papiernik, Liliane G. Hubert-pfalzgraf, Bernard Septe and Jacqueline Vaissermann

Abstract

The molecular constitution of solutions containing niobium alkoxides and divalent metal acetates M(OAc)2 (M=Mg, Ba, Pb, Zn, Cd) has been examined. The heterometallic aggregates MNb2(µ-OAc)2(µ-OPri)4(OPri)6 (M=Mg 1, Cd 2, Pb 3a) have been isolated and characterized by elemental analysis, FTIR, multinuclear NMR (1H, 13C, 207Pb, 113Cd) and by single-crystal X-ray diffraction for M=Mg and Cd. The magnesium derivative crystallizes in the monoclinic system, space group P21 /c with the unit-cell parameters a=21.238(5), b=10.127(10), c=24.861(3) Å, β=107.77(2)° and Z=4. The thermal stability of the various species has been investigated. Condensation is induced thermally for PbNb2(OAc)2(OPri)10 . The reactivity between MNb2(µ-OAc)2- (µ-OPri)4(OPri)6 (M=Pb, Mg) and other metallic species has been evaluated. A terheterometallic compound, PbMgNb2O(OAc)2(OPri)10 has been isolated. Whereas no reaction is observed between Ba(OAc)2 and Nb(OPri)5 , the reaction between metal alkoxides affords BaNb2(OPri)12(PriOH)2 . Its reactivity shows that the absence of an assembling acetate ligand induces facile separation between the metals. Results of the hydrolysis experiments of 1–3a are given. The powders have been analyzed by TG, SEM–EDX, light scattering and XRD. The merit of the assembling acetate ligand for avoiding the segregation of the metals is emphasized.

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