Studies of the oxovanadium-organophosphonate system: Hydrothermal synthesis and crystal structure of the mixed valence cluster

José Salta, Jon Zubieta

Research output: Contribution to journalReview article

4 Scopus citations

Abstract

The room temperature reaction of (Bu4N)3V5O14 with PhPO3H2 in methanol yields the pentanuclear V(V) cluster (Bu4N)[V5O7(OCH3) 2(PhPO3)5]· CH3OH (1·CH3OH). In contrast, the hydrothermal reaction of (Ph4P) [VO2Cl2], PhPO3H2 and (NH4)H2PO4 at 125°C for 96 hr yields the mixed valence V(IV)/V(V) species (Ph4P)2[V5O9(PhPO3) 3(PhPO3H)2] (3). While the anions of both 1 and 3 exhibit a pentanuclear core, the structural consequences of 1-electron reduction of the fully oxidized cluster of 1 to produce 3 are quite dramatic, including reduction in coordination numbers at two vanadium sites and protonation of two phosphonate oxygen sites with concomitant structural reorganization. Crystal data: 1, monoclinic P21/n, a = 12.167(2) Å, b = 23.348(5) Å, c = 22.508(5) Å, β = 98.49(2)°, V = 6323.9(19) Å3, Z = 4, Dcalc = 1.558 g cm-3; 3, triclinic, P1, a = 13.478(3) Å, b = 14.399(3) Å, c = 23.638(5) Å, α = 72.53(2)°, β = 85.58(2)°, γ = 69.88(4)°, V = 4107.0(16) Å3, Z = 2, Dcalc = 1.479 g cm-3.

Original languageEnglish (US)
Pages (from-to)361-380
Number of pages20
JournalJournal of Cluster Science
Volume8
Issue number3
DOIs
StatePublished - Sep 1997

Keywords

  • Metal oxide clusters
  • Mixed valence compounds
  • Oxovanadium phosphonate clusters

ASJC Scopus subject areas

  • Biochemistry
  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

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