Oxovanadium alkoxide complexes. Syntheses and crystal structures of (Ph4P)2[(VO)2Cl4(OR)2] (R = -CH3, -CH2CH2Cl) and [(VO)2Cl2{MeC(CH2OH) (CH2O)2}2]

José Salta, Jon Zubieta

Research output: Contribution to journalArticle

16 Scopus citations

Abstract

The reactions of (Ph4P) [VO2Cl2] in various alcohols yield complexes of the type (Ph4P)2[(VO)2Cl4(OR)2] (R = -CH3 (1),-CH2CH2Cl (2)). Similarly, the reaction of (BzPh3P) [VO2Cl2] with tris(hydroxymethyl)ethane yields [(VO)2Cl2{MeC(CH2OH) (CH2O)2}2]· 2BzPh3PCl·2CH3OH (3·2BzPh3PCl·2CH3OH). The molecular anions of complexes 1 and 2 consist of binuclear units of edge-sharing V(IV) square pyramids. The alkoxy groups bridge the two V(V) sites and the {V=O} groups adopt the anti-orientation with respect to the (V2O2) rhombus of the bridging unit. In contrast, the neutral [(VO)2Cl2{MeC(CH2OH) (CH2O)2}2] consists of the edge-sharing V(V) octahedra. The tridentate ligands each provide one alkoxy oxygen adopting a bridging mode between V(V) sites, an alkoxy oxygen as a terminal ligand to one V(V) site and an alcohol oxygen donor as a terminal ligand to the other V(V) site. The terminal oxo-groups occupy positions approximately coplanar to the {V2O2} rhombus of the bridging unit. Crystal data: (Ph4P)2[(VO)2Cl4(OCH 3)2]·2CH3OH (1·2CH3OH), monoclinic P21/n, a = 12.068(2), b = 16.388(3), c = 12.893(3) Å, β = 100.72(2)°, Z = 2. (Ph4P)2[(VO)2Cl4-(OCH 2CH2Cl)2] (2), triclinic P1, a = 11.227(2), b = 12.496(2), c = 10.609(2) Å, α = 109.78(2), β = 114.68(3), γ = 85.46(3)°, Z = 1. [(VO)2Cl2{MeC(CH2OH) (CH2O)2}2]·2BzPh 3PCl·2CH3OH (3·2BzPh3PCl·2CH3OH), triclinic P1, a = 10.316(2), b = 15.762(3), c = 10.125(2) Å, α = 105.72(3), β = 90.02(3), γ = 79.86(3)°, Z = 1.

Original languageEnglish (US)
Pages (from-to)83-88
Number of pages6
JournalInorganica Chimica Acta
Volume257
Issue number1
DOIs
StatePublished - Apr 1 1997

Keywords

  • Alkoxide complexes
  • Crystal structures
  • Oxo complexes
  • Vanadium complexes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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