Asymmetric Alkylidene and Oxo Complexes of Tungsten(VI)

Joseph A. Heppert, Steven D. Dietz, Nancy W. Eilerts, Robert W. Henning, Martha D. Morton, Fusao Takusagawa, Frank A. Kaul

Research output: Contribution to journalArticle

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Abstract

Reactions between (t-BuO)3W(CR) derivatives and 1,1′-bi-2-naphthols (H2R2BINO, R = Me, Br, Ph) generate mononuclear C1-symmetric (R2BINO)(t-BuO)2W(CHR) complexes. An analogous reaction with 2 equiv of H2Me2BINO generates (Me2BINO)2W(CHPh), while a reaction between H2Me2BINO and (t-BuO)4W(O) produces (Me2BINO)(t-BuO)2W(O). This oxo complex was characterized by X-ray crystallography, which shows it to be a highly-distorted trigonal bipyramidal complex in which the Me2BINO ligand adopts a λ chelate stereochemistry. Although the complexes show little stereoselectivity in Wittig-like alkylidene transfer to benzaldehyde, the ring opening metathesis polymerization of norbornene proceeds with modest stereoselectivity. The fraction of cis-polynorbornene increases in concert with the steric demands of the substituents on the R2BINO ligand. Crystal data for (Me2BINO)(t-BuO)2W(O) at 113 K: a = 11.426(3) Å, b = 14.733(3) Å, c = 16.716(4) Å, β = 105.87(2)°, Z = 4, Dcalc. = 1.616, space group P21/n (No. 14), R(F) = 0.053, Rw(F) = 0.106 for 3451 reflections (Fo > 0).

Original languageEnglish (US)
Pages (from-to)2565-2572
Number of pages8
JournalOrganometallics
Volume12
Issue number7
DOIs
StatePublished - Jan 1 1993
Externally publishedYes

Fingerprint

alkylidene
Stereoselectivity
Tungsten
tungsten
Ligands
Stereochemistry
X ray crystallography
Ring opening polymerization
ligands
metathesis
stereochemistry
Derivatives
chelates
Crystals
crystallography
polymerization
rings
crystals
x rays
2-naphthol

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Heppert, J. A., Dietz, S. D., Eilerts, N. W., Henning, R. W., Morton, M. D., Takusagawa, F., & Kaul, F. A. (1993). Asymmetric Alkylidene and Oxo Complexes of Tungsten(VI). Organometallics, 12(7), 2565-2572. https://doi.org/10.1021/om00031a029

Asymmetric Alkylidene and Oxo Complexes of Tungsten(VI). / Heppert, Joseph A.; Dietz, Steven D.; Eilerts, Nancy W.; Henning, Robert W.; Morton, Martha D.; Takusagawa, Fusao; Kaul, Frank A.

In: Organometallics, Vol. 12, No. 7, 01.01.1993, p. 2565-2572.

Research output: Contribution to journalArticle

Heppert, JA, Dietz, SD, Eilerts, NW, Henning, RW, Morton, MD, Takusagawa, F & Kaul, FA 1993, 'Asymmetric Alkylidene and Oxo Complexes of Tungsten(VI)', Organometallics, vol. 12, no. 7, pp. 2565-2572. https://doi.org/10.1021/om00031a029
Heppert JA, Dietz SD, Eilerts NW, Henning RW, Morton MD, Takusagawa F et al. Asymmetric Alkylidene and Oxo Complexes of Tungsten(VI). Organometallics. 1993 Jan 1;12(7):2565-2572. https://doi.org/10.1021/om00031a029
Heppert, Joseph A. ; Dietz, Steven D. ; Eilerts, Nancy W. ; Henning, Robert W. ; Morton, Martha D. ; Takusagawa, Fusao ; Kaul, Frank A. / Asymmetric Alkylidene and Oxo Complexes of Tungsten(VI). In: Organometallics. 1993 ; Vol. 12, No. 7. pp. 2565-2572.
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abstract = "Reactions between (t-BuO)3W(CR) derivatives and 1,1′-bi-2-naphthols (H2R2BINO, R = Me, Br, Ph) generate mononuclear C1-symmetric (R2BINO)(t-BuO)2W(CHR) complexes. An analogous reaction with 2 equiv of H2Me2BINO generates (Me2BINO)2W(CHPh), while a reaction between H2Me2BINO and (t-BuO)4W(O) produces (Me2BINO)(t-BuO)2W(O). This oxo complex was characterized by X-ray crystallography, which shows it to be a highly-distorted trigonal bipyramidal complex in which the Me2BINO ligand adopts a λ chelate stereochemistry. Although the complexes show little stereoselectivity in Wittig-like alkylidene transfer to benzaldehyde, the ring opening metathesis polymerization of norbornene proceeds with modest stereoselectivity. The fraction of cis-polynorbornene increases in concert with the steric demands of the substituents on the R2BINO ligand. Crystal data for (Me2BINO)(t-BuO)2W(O) at 113 K: a = 11.426(3) {\AA}, b = 14.733(3) {\AA}, c = 16.716(4) {\AA}, β = 105.87(2)°, Z = 4, Dcalc. = 1.616, space group P21/n (No. 14), R(F) = 0.053, Rw(F) = 0.106 for 3451 reflections (Fo > 0).",
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AU - Dietz, Steven D.

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N2 - Reactions between (t-BuO)3W(CR) derivatives and 1,1′-bi-2-naphthols (H2R2BINO, R = Me, Br, Ph) generate mononuclear C1-symmetric (R2BINO)(t-BuO)2W(CHR) complexes. An analogous reaction with 2 equiv of H2Me2BINO generates (Me2BINO)2W(CHPh), while a reaction between H2Me2BINO and (t-BuO)4W(O) produces (Me2BINO)(t-BuO)2W(O). This oxo complex was characterized by X-ray crystallography, which shows it to be a highly-distorted trigonal bipyramidal complex in which the Me2BINO ligand adopts a λ chelate stereochemistry. Although the complexes show little stereoselectivity in Wittig-like alkylidene transfer to benzaldehyde, the ring opening metathesis polymerization of norbornene proceeds with modest stereoselectivity. The fraction of cis-polynorbornene increases in concert with the steric demands of the substituents on the R2BINO ligand. Crystal data for (Me2BINO)(t-BuO)2W(O) at 113 K: a = 11.426(3) Å, b = 14.733(3) Å, c = 16.716(4) Å, β = 105.87(2)°, Z = 4, Dcalc. = 1.616, space group P21/n (No. 14), R(F) = 0.053, Rw(F) = 0.106 for 3451 reflections (Fo > 0).

AB - Reactions between (t-BuO)3W(CR) derivatives and 1,1′-bi-2-naphthols (H2R2BINO, R = Me, Br, Ph) generate mononuclear C1-symmetric (R2BINO)(t-BuO)2W(CHR) complexes. An analogous reaction with 2 equiv of H2Me2BINO generates (Me2BINO)2W(CHPh), while a reaction between H2Me2BINO and (t-BuO)4W(O) produces (Me2BINO)(t-BuO)2W(O). This oxo complex was characterized by X-ray crystallography, which shows it to be a highly-distorted trigonal bipyramidal complex in which the Me2BINO ligand adopts a λ chelate stereochemistry. Although the complexes show little stereoselectivity in Wittig-like alkylidene transfer to benzaldehyde, the ring opening metathesis polymerization of norbornene proceeds with modest stereoselectivity. The fraction of cis-polynorbornene increases in concert with the steric demands of the substituents on the R2BINO ligand. Crystal data for (Me2BINO)(t-BuO)2W(O) at 113 K: a = 11.426(3) Å, b = 14.733(3) Å, c = 16.716(4) Å, β = 105.87(2)°, Z = 4, Dcalc. = 1.616, space group P21/n (No. 14), R(F) = 0.053, Rw(F) = 0.106 for 3451 reflections (Fo > 0).

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