A templated synthesis of tetranuclear polyoxoalkoxymolybdates(V). Bromo coordinated oxomolybdenum(V) clusters: Known core structure with new ligands. Oxidation to the Lindquist anion

Barbara Modec, Jurij V. Brenčič, Jon Zubieta

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Abstract

Reactions of (PyH)2[MoOCl5] and (PyH)[MoOBr4] with alcohols in the presence of tetramethylpyrazine have inadvertently resulted in a series of tetranuclear polyoxoalkoxymolybdates(V) with the general formula (PyH)2-[Mo4O8(OR)2(HOR) 2X4] (1a: R = Me, X = Cl; 1b: R = Et, X = Cl; 1c: R = Et, X = Br). Reaction with the nitrogen donor ligand pyridine (Py = C5H5N), run under similar conditions, afforded neutral cluster [Mo4O8(OEt)2Br2Py4]2a, which also crystallizes as an acetonitrile solvate, [Mo4O8(OEt)2Br2Py4] ·2CH3CN 2b. The compounds were characterized by single crystal X-ray diffraction studies. All five tetranuclear clusters contain as a common feature the {Mo4O4-(μ3-O)2(μ-O) 2(μ-OR)2}2+ core onto whose periphery different terminal ligands are attached. The core structure may be viewed as the fusion of two well-defined {Mo2O4}2+ building blocks bridged through oxo groups. The {Mo2O4}2+ clusters with coordinated bromo ligands are the first of this type to be structurally characterized. Introduction of water resulted in a fully oxidized [LH2][Mo6O19]·L·2EtOH 3 (L= tetramethylpyrazine) whose structure consists of Lindquist anions trapped in the vacancies between the intertwined organic chains with the LH22+···ethanol·· ·L repeating unit.

Original languageEnglish (US)
Pages (from-to)1500-1507
Number of pages8
JournalJournal of the Chemical Society, Dalton Transactions
Issue number7
StatePublished - Apr 20 2002

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ASJC Scopus subject areas

  • Chemistry(all)

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