DOI: 10.1002/anie.199206281. A Cyclometalated Aryloxy(chloro)neopentylidenetungsten Complex: A Highly Active and Stereoselective Catalyst for the Metathesis of <i>cis</i>‐ and <i>trans</i>‐2‐Pentene, Norbornene, 1‐Methyl‐norbornene, and Ethyl Oleate

A Cyclometalated Aryloxy(chloro)neopentylidenetungsten Complex: A Highly Active and Stereoselective Catalyst for the Metathesis of cis‐ and trans‐2‐Pentene, Norbornene, 1‐Methyl‐norbornene, and Ethyl Oleate

10.1002/anie.199206281

Crossref journal-article

Wiley

Angewandte Chemie International Edition in English (311)

Bibliography

Couturier, J., Paillet, C., Leconte, M., Basset, J., & Weiss, K. (1992). A Cyclometalated Aryloxy(chloro)neopentylidenetungsten Complex: A Highly Active and Stereoselective Catalyst for the Metathesis of cisâ and transâ2âPentene, Norbornene, 1âMethylânorbornene, and Ethyl Oleate. Angewandte Chemie International Edition in English, 31(5), 628â631. Portico.

Authors 5

Jean‐Luc Couturier (first)
Christophe Paillet (additional)
Michel Leconte (additional)
Jean‐Marie Basset (additional)
Karin Weiss (additional)

References 31 Referenced 104

{'key': 'e_1_2_1_1_2', 'volume-title': 'Olefin Metathesis', 'author': 'Ivin K. J.', 'year': '1983'} / Olefin Metathesis by Ivin K. J. (1983)
10.1007/978-94-011-3328-9_1
(a)J.Kress M.Wesolek J. A.Osborn J. Chem. Soc. Chem. Commun.1982 514–516; (10.1039/c39820000514)
10.1016/0304-5102(86)85097-0
10.1021/ja00270a056
F.Quignard M.Leconte J.‐M.Basset J. Chem. Soc. Chem. Commun.1985 1816–1817.
(a)J.‐M.Basset M.Leconte J.Ollivier F.Quignard Fr. Pat. 8309876 1983 SNEA US‐Pat. 4550216 1985 SNEA;
(b) Fr. Pat. 8501930 1985 SNEA US‐Pat. 4654462 1987 SNEA;
(c) Fr. Pat. 8611978 1986 SNEA US‐Pat. 4861848 1989 SNEA;
10.1016/0304-5102(85)87014-0
10.1016/0304-5102(86)85098-2
10.1021/om00072a018
10.1002/9780470132579.ch10
10.1021/ic00272a026
In our first study [4] we found that reaction of one equivalent of MgNp2with [WCl4(O–2 6–C6H3Ph2)2] in Et2O led to a compoundA1whose1H NMR spectrum (CDCl3) showed a signal at δ = 8.7 for a hydrogen atom bound to a carbene;A1proved essentially inactive in the metathesis ofcis‐2‐pentene. We have now some indications that suggest thatA1is a dimeric neopentylidene species (not yet totally identified) resulting from the dimerization of1aor1b. This dimerization seems to be rather fast in solution (especially in CHCl3and CH2Cl2) but can also be observed in the solid state where the reaction is slower.
Characteristic1H (100 MHz) and13C (25 MHz) NMR data for1a(C6D6 25°C): δ(W = CHCMe3) = 10.11 (JW H= 14 Hz) δ(W = CHCMe3) = 0.57; δ(W = CH) = 296.66 (JC H) =130.5 (JC W= 166 Hz) δ(WCipso) =183.15 (JC W=115 Hz) δ(W = CHCMe3) = 45.24 δ(W = CHCMe3) = 31.82. The corresponding data for1bare practically identical.
10.1021/om00088a018
10.1021/om00158a025
10.1021/ja00253a041
10.1021/om00098a030
10.1021/om00108a010
10.1021/ja00235a031
For the metathesis ofcis‐2‐pentene the stereoselectivity at 0% conversion is accurately determined by plotting thetrans/cisratio of 2‐butene vs. thetrans /cisratio of 2‐pentene and by extrapolating attrans/cis‐2‐pentene = 0 (in the case oftrans‐2‐pentene cis/transC4is plotted vs.cis/transC5).[15]
10.1021/ja00518a027
The catalyst is deactivated by addition of benzaldehyde; polynorbornene is recovered after addition of THF to the reaction mixture precipitation with methanol filtration and drying.
{'key': 'e_1_2_1_17_2', 'first-page': '695', 'volume-title': 'Transition Metal Catalyzed Polymerizations: Ziegler‐Natta and Metathesis Polymerizations', 'author': 'Boutarfa Dj.', 'year': '1988'} / Transition Metal Catalyzed Polymerizations: Ziegler‐Natta and Metathesis Polymerizations by Boutarfa Dj. (1988)
The 100% head‐tail 100%cisstructure of the poly‐1‐methylnorbornene obtained with1aor1bwas deduced from1H and13C NMR spectra of the polymer;[19]13C{1H} NMR (62.8 MHz CDCl3): δ = 29.29 (C‐8) 33.02 (C‐5) 38.14 (C‐4) 41.82 (C‐6) 44.13 (C‐1) 50.02 (C‐7) 135.08 (C‐3) 139.47 (C‐2) (see Scheme 3 for the numbering of the carbon atoms). The predominantly syndiotactic structure was deduced from the13C NMR spectrum of the hydrogenated polymer [19]
10.1002/pi.4980160106
10.1007/978-94-011-3328-9_2
Ethyl oleate (Sigma 99%) was used immediately after the ampules were opened and the contents purified by passage through a column of activated alumina.
10.1016/0304-5102(91)85091-F

Dates

Type	When
Created	21 years, 8 months ago (Dec. 30, 2003, 6:11 p.m.)
Deposited	1 year, 10 months ago (Oct. 23, 2023, 9:12 a.m.)
Indexed	4 weeks ago (Aug. 5, 2025, 8:40 a.m.)
Issued	33 years, 4 months ago (May 1, 1992)
Published	33 years, 4 months ago (May 1, 1992)
Published Online	21 years, 8 months ago (Dec. 22, 2003)
Published Print	33 years, 4 months ago (May 1, 1992)

Funders 0

None

BibTeX

@article{Couturier_1992, title={A Cyclometalated Aryloxy(chloro)neopentylidenetungsten Complex: A Highly Active and Stereoselective Catalyst for the Metathesis of cis‐ and trans‐2‐Pentene, Norbornene, 1‐Methyl‐norbornene, and Ethyl Oleate}, volume={31}, ISSN={0570-0833}, url={http://dx.doi.org/10.1002/anie.199206281}, DOI={10.1002/anie.199206281}, number={5}, journal={Angewandte Chemie International Edition in English}, publisher={Wiley}, author={Couturier, Jean‐Luc and Paillet, Christophe and Leconte, Michel and Basset, Jean‐Marie and Weiss, Karin}, year={1992}, month=may, pages={628–631} }

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