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

doi:10.1021/om00031a029

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 journal › Article › peer-review

20 Scopus citations

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, D_calc. = 1.616, space group P2₁/n (No. 14), R(F) = 0.053, R_w(F) = 0.106 for 3451 reflections (F_o > 0).

Original language	English (US)
Pages (from-to)	2565-2572
Number of pages	8
Journal	Organometallics
Volume	12
Issue number	7
DOIs	https://doi.org/10.1021/om00031a029
State	Published - 1993
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1021/om00031a029

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@article{4f7b3fc5eda6491f9d4e175b2cf04472,

title = "Asymmetric Alkylidene and Oxo Complexes of Tungsten(VI)",

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).",

author = "Heppert, {Joseph A.} and Dietz, {Steven D.} and Eilerts, {Nancy W.} and Henning, {Robert W.} and Morton, {Martha D.} and Fusao Takusagawa and Kaul, {Frank A.}",

year = "1993",

doi = "10.1021/om00031a029",

language = "English (US)",

volume = "12",

pages = "2565--2572",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "7",

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TY - JOUR

T1 - Asymmetric Alkylidene and Oxo Complexes of Tungsten(VI)

AU - Heppert, Joseph A.

AU - Dietz, Steven D.

AU - Eilerts, Nancy W.

AU - Henning, Robert W.

AU - Morton, Martha D.

AU - Takusagawa, Fusao

AU - Kaul, Frank A.

PY - 1993

Y1 - 1993

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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U2 - 10.1021/om00031a029

DO - 10.1021/om00031a029

M3 - Article

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VL - 12

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JO - Organometallics

JF - Organometallics

IS - 7

ER -

Asymmetric Alkylidene and Oxo Complexes of Tungsten(VI)

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