Highly Oxidizing Organometallics: Physicochemical Characterization of (MethylcyclopentadienyOvanadium(Ilf) Trichloride and Related Vanadium(III) and Titanium(III) Derivatives

David B. Morse, David N. Hendrickson, Thomas Rauchfuss, Scott R. Wilson

Research output: Contribution to journalArticlepeer-review

Abstract

The compound (MeCp)VCl3 (1) (Cp = η-C5H5) may be synthesized in high yield and purity from (MeCp)2VCl2 and SOCl2. Compound 1 crystallizes in the space group P1 with cell dimensions a = 6.860 (2) Å, b = 11.037 (4) Å, c = 6.832 (2) Å, α = 97.37 (3)°, β = 118.77 (2)°, γ = 80.73 (3)°, and Z = 2; Rw = 0.087, R = 0.069 for 1860 Mo Kα data with I > 2.85σ(I). Vanadium-chlorine bond lengths range from 2.187 (4) to 2.208 (4) Å and the mean V-Cp distance is 1.93 (1) Å. Compound 1 undergoes a reversible reduction at +425 mV (Ag/AgCl), which may be compared with (MeCp)VOCl2 (+270 mV) and (MeCp)TiCl3 (-355 mV). Compound 1 shows a well-resolved paramagnetically shifted 1H NMR spectrum. In comparison with the 1H NMR signals of isoelectronic [Cp2Co][(MeCp)TiCl3], those observed for 1 indicate more covalent M-Cp interactions in 1 than in [Cp2Co][(MeCp)TiCl3]. Magnetic susceptibility measurements on solid [Cp2Co][(MeCp)VCl3] indicate a zero field splitting value of 8 cm-1.

Original languageEnglish (US)
Pages (from-to)496-502
Number of pages7
JournalOrganometallics
Volume7
Issue number2
DOIs
StatePublished - Feb 1 1988

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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