Polyoxoanion Coordination Chemistry: Synthesis and Characterization of the Heterometallic, Hexanuclear Clusters [{Zn(bipy)2}2V4O 12]·[{Zn(phen)2}2V4O 12]·H2O, and [{Ni(bipy)2}2Mo4O14]

Yiping Zhang, Pamela J. Zapf, Linda M. Meyer, Robert C. Haushalter, Jon Zubieta

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Abstract

The hydrothermal reactions of vanadium oxide and molybdenum oxide starting materials with divalent first-row transition metal cations in the presence of nitrogen donor chelating ligands yield the heterometallic hexanuclear clusters [{Zn(bipy)2}2V4O12] (2), [{Zn(phen)2}2V4O12]·H 2O (3·H2O), and [{Ni(bipy)2}2Mo4O14] (4). A similar reaction in the presence of excess 2,2′-bipyridine yields [Zn(bipy)3]2[V4O12]·11H 2O (1·11H2O), a species with an isolated {V4O12}4- cluster. The structure of 2 consists of a {V4O12}4- ring covalently attached to each of two {Zn(bipy)2}2+ moieties through the terminal oxo groups of alternate vanadium sites. In contrast, the structure of 3 exhibits a {V4O12}4- ring linked through oxo groups of adjacent vanadium sites to two {Zn(phen)2}2+ moieties. The structure of 4 is constructed from two {Mo2O7}2- units linked through two {Ni(bipy)2}2+ groups to form a cyclic 12-membered {Mo4Ni2O6} core. Crystal data: [Zn(bipy)3]2[V4O12]·11H 2O (1·11H2O), a = 21.910(4) Å, b = 14.044(2) Å, c = 23.815(4) Å, β= 106.15(1)°, monoclinic, C2/c, Z = 4; [{Zn(bipy)2}2V4O12] (2), a = 12.017(2) Å, c = 15.120(2) Å, tetragonal P42/n, Z = 2, [{Zn(o-phen)2}2V4O12]·H 2O (3·H2O), a = 18.182(2) Å, b = 11.3668(9) Å, c = 23.455(2) Å, β= 97.815(7)°, monoclinic P21/c, Z = 4; [{Ni(bipy)2{2Mo4O14] (4), a = 12.323(2) Å, c = 14.897(4) Å, tetragonal P42212, Z = 2.

Original languageEnglish (US)
Pages (from-to)2159-2165
Number of pages7
JournalInorganic Chemistry
Volume36
Issue number10
DOIs
StatePublished - 1997

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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