Aryloxide Ligands in the Metathesis of Olefins: Syntheses of W(OAr)xCl6_xComplexes With X = 2, 3, And 4. Crystal Structures of W(O-2,6-C6H3-i-Pr2)3cl3and W(O-2,6-C6H3Ph2)2Cl4

Francoise Quignard, Michel Leconte, Jean-Marie Maurice Basset, Leh Yeh Hsu, John J. Alexander, Sheldon G. Shore*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

72 Scopus citations

Abstract

Syntheses and characterization of three families of aryloxide complexes of W(VI), which are useful precursors for metathesis of olefins, are reported: W(OAr)x(Cl)6-x(x = 2, 3, 4). The structures of Cl3W(O-2,6-C6H3-i-Pr2)3and Cl4W(O-2,6-C6H3Ph2)2are described. Both complexes have slightly distorted octahedral coordination spheres. For the structure of Cl3W(O-2,6-C6H3-i-Pr2)3, the chlorines occupy the meridional sites, while in the case of Cl4W(0-2,6-C6H3Ph2)2, the OC6H3Ph2groups are cis to each other. Crystal data for Cl3W(O-2,6-C6H3-i-Pr2)3: space group P21/n, monoclinic, a = 13.446 (2) Å, b = 17.824 (4) Å, c = 16.289 (3) Å, β = 99.55 (1)°, V = 3851 Å3, mol wt 882.02,Pcalcd=1.418 g cm-3for Z = 4. For Mo Ka 7164 unique reflections were collected at 298 K over the range 4° ≤ 2θ ≤ 50° with 5582 reflections > 3σ-(I) used in the final refinement. RF= 0.023 and RwF= 0.031. Crystal data for Cl4W(O-2,6-C6H3Ph2)2.1/2C7H8: space group P1, triclinic, a = 10.547 (3) Å, b = 13.669 (1) Å, c = 14.632 (1) Å, a = 84.89 (2)°, β = 78.34 (1)°, γ = 83.48 (2)°, V = 2062 A3, mol wt 816.26,Pcalcd= 1.317 g cm-3for Z = 2. For Mo Ka 2915 reflections were collected at 298 K over the range 4° ≤2θ ≤ 40° with 2588 reflections ≥3σ(I) used in the final refinement. Rf= 0.058 and Rwf= 0.094.

Original languageEnglish (US)
Pages (from-to)4272-4277
Number of pages6
JournalInorganic Chemistry
Volume26
Issue number25
DOIs
StatePublished - Dec 1 1987

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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