Synthesis and Catalytic Evaluation in Olefin Metathesis of a Second-Generation Homobimetallic Ruthenium-Arene Complex Bearing a Vinylidene Ligand

[en] The new homobimetallic ruthenium–vinylidene complex [(p-cymene)Ru(μ-Cl)3RuCl(═C═CHPh)(IMes)] (6) was isolated in high yield upon treatment of [(p-cymene)Ru(μ-Cl)3RuCl(η2-C2H4)(IMes)] (5) with a slight excess of phenylacetylene at −50 °C. Although it was very stable under normal atmosphere in the solid state, this product underwent an oxidative cleavage into the corresponding carbonyl compound [(p-cymene)Ru(μ-Cl)3RuCl(CO)(IMes)] (7) when dissolved in oxygen-containing solvents. Second-generation complexes 6 and 7 were characterized by IR and NMR spectroscopies, and their molecular structures were determined by X-ray diffraction analysis. The catalytic activity of complex 6 was probed in various types of olefin metathesis reactions. Compared to its first-generation analogue [(p-cymene)Ru(μ-Cl)3RuCl(═C═CHPh)(PCy3)], the new ruthenium initiator displayed an enhanced activity. It was also much more selective than ruthenium–ethylene complex 5. Aluminum chloride was a valuable cocatalyst for the ROMP of cyclooctene, whereas phenylacetylene was better suited to achieve the fast and quantitative RCM of α,ω-dienes into the corresponding di- or trisubstituted cycloolefins. The role of the terminal alkyne was rationalized by assuming that it would allow an enyne metathesis to take place, thereby transforming saturated vinylidene precursor 6 into a highly active mono- or bimetallic ruthenium–alkylidene species.

Disciplines :

Chemistry

Author, co-author :

Borguet, Yannick ; Université de Liège - ULiège > Département de chimie (sciences) > Chimie macromoléculaire et catalyse organique

Sauvage, Xavier ; Université de Liège - ULiège > Centre de recherches du cyclotron

Zaragoza, Guillermo

Demonceau, Albert ; Université de Liège - ULiège > Département de chimie (sciences) > Chimie macromoléculaire et catalyse organique

Delaude, Lionel ; Université de Liège - ULiège > Département de chimie (sciences) > Chimie macromoléculaire et catalyse organique

Language :

English

Title :

Synthesis and Catalytic Evaluation in Olefin Metathesis of a Second-Generation Homobimetallic Ruthenium-Arene Complex Bearing a Vinylidene Ligand

Publication date :

2011

Journal title :

Organometallics

ISSN :

0276-7333

eISSN :

1520-6041

Publisher :

American Chemical Society, Washington, United States - District of Columbia

Volume :

Issue :

Pages :

2730-2738

Peer reviewed :

Peer Reviewed verified by ORBi

Available on ORBi :

since 24 June 2011

Statistics

Number of views

135 (14 by ULiège)

Number of downloads

2 (2 by ULiège)

More statistics

Scopus citations^®

Scopus citations^®
without self-citations

OpenCitations

OpenAlex citations

See more details

publications

supporting

mentioning

contrasting

Smart Citations

Citing PublicationsSupportingMentioningContrasting

View Citations

See how this article has been cited at scite.ai

scite shows how a scientific paper has been cited by providing the context of the citation, a classification describing whether it supports, mentions, or contrasts the cited claim, and a label indicating in which section the citation was made.

Bibliography

Grubbs, R. H.; Miller, S. J.; Fu, G. C. Acc. Chem. Res. 1995, 28, 446-452
Grubbs, R. H. Tetrahedron 2004, 60, 7117-7140
Grubbs, R. H. Adv. Synth. Catal. 2007, 349, 34-40
For monographs, see: Ivin, K. J.; Mol, J. C. Olefin Metathesis and Metathesis Polymerization; Academic Press: San Diego, 1997.
Handbook of Metathesis; Grubbs, R. H., Ed.; Wiley-VCH: Weinheim, 2003.
Green Metathesis Chemistry; Dragutan, V.; Demonceau, A.; Dragutan, I.; Finkelshtein, E. S., Eds.; NATO Science for Peace and Security Series A: Chemistry and Biology; Springer: Dordrecht, 2010.
Diesendruck, C. E.; Tzur, E.; Lemcoff, N. G. Eur. J. Inorg. Chem. 2009, 4185-4203
Dragutan, V.; Dragutan, I. Platinum Met. Rev. 2004, 48, 148-153
Katayama, H.; Ozawa, F. Coord. Chem. Rev. 2004, 248, 1703-1715
Bruneau, C.; Dixneuf, P. H. Angew. Chem., Int. Ed. 2006, 45, 2176-2203.
Metal Vinylidenes and Allenylidenes in Catalysis; Bruneau, C.; Dixneuf, P. H., Eds.; Wiley-VCH: Weinheim, 2008.
Lozano-Vila, A.; Monsaert, S.; Bajek, A.; Verpoort, F. Chem. Rev. 2010, 110, 4865-4909
Dragutan, I.; Dragutan, V. Platinum Met. Rev. 2006, 50, 81-97
Dragutan, V.; Dragutan, I.; Verpoort, F. Platinum Met. Rev. 2005, 49, 33-40
Boeda, F.; Clavier, H.; Nolan, S. P. Chem. Commun. 2008, 2726-2740
Colacino, E.; Martinez, J.; Lamaty, F. Coord. Chem. Rev. 2007, 251, 726-764
Samojaowicz, C.; Bieniek, M.; Grela, K. Chem. Rev. 2009, 109, 3708-3742
Vougioukalakis, G. C.; Grubbs, R. H. Chem. Rev. 2010, 110, 1746-1787
For monographs, see: Beligny, S.; Blechert, S. In N-Heterocyclic Carbenes in Synthesis; Nolan, S. P., Ed.; Wiley-VCH: Weinheim, 2006; pp 1-25.
Despagnet-Ayoub, E.; Ritter, T. In N-Heterocyclic Carbenes in Transition Metal Catalysis; Glorius, F., Ed.; Topics in Organometallic Chemistry, Vol. 21; Springer: Berlin, 2007; pp 193-218.
Delaude, L.; Demonceau, A. In N-Heterocyclic Carbenes. From Laboratory Curiosities to Efficient Synthetic Tools; Díez-González, S., Ed.; RSC Catalysis Series, Vol. 6; The Royal Society of Chemistry: Cambridge, 2010; pp 196-227.
Louie, J.; Grubbs, R. H. Angew. Chem., Int. Ed. 2001, 40, 247-249
Opstal, T.; Verpoort, F. J. Mol. Catal. A: Chem. 2003, 200, 49-61
Sémeril, D.; Bruneau, C.; Dixneuf, P. H. Helv. Chim. Acta 2001, 84, 3335-3341
Quebatte, L.; Solari, E.; Scopelliti, R.; Severin, K. Organometallics 2005, 24, 1404-1406
Sauvage, X.; Borguet, Y.; Noels, A. F.; Delaude, L.; Demonceau, A. Adv. Synth. Catal. 2007, 349, 255-265
Solari, E.; Antonijevic, S.; Gauthier, S.; Scopelliti, R.; Severin, K. Eur. J. Inorg. Chem. 2007, 367-371
Borguet, Y.; Sauvage, X.; Zaragoza, G.; Demonceau, A.; Delaude, L. Organometallics 2010, 29, 6675-6686
Delaude, L.; Demonceau, A.; Noels, A. F. Chem. Commun. 2001, 986-987
Delaude, L.; Szypa, M.; Demonceau, A.; Noels, A. F. Adv. Synth. Catal. 2002, 344, 749-756
Delaude, L.; Demonceau, A.; Noels, A. F. Curr. Org. Chem. 2006, 10, 203-215
Delaude, L.; Delfosse, S.; Richel, A.; Demonceau, A.; Noels, A. F. Chem. Commun. 2003, 1526-1527
Richel, A.; Delfosse, S.; Cremasco, C.; Delaude, L.; Demonceau, A.; Noels, A. F. Tetrahedron Lett. 2003, 44, 6011-6015
Wakatsuki, Y. J. Organomet. Chem. 2004, 689, 4092-4109
For comparative studies on the donor strengths of phosphine and NHC ligands, see: Chianese, A. R.; Li, X.; Janzen, M. C.; Faller, J. W.; Crabtree, R. H. Organometallics 2003, 22, 1663-1667
Chianese, A. R.; Kovacevic, A.; Zeglis, B. M.; Faller, J. W.; Crabtree, R. H. Organometallics 2004, 23, 2461-2468
Fürstner, A.; Alcarazo, M.; Krause, H.; Lehmann, C. W. J. Am. Chem. Soc. 2007, 129, 12676-12677
Kelly, R. A., III; Clavier, H.; Giudice, S.; Scott, N. M.; Stevens, E. D.; Bordner, J.; Samardjiev, I.; Hoff, C. D.; Cavallo, L.; Nolan, S. P. Organometallics 2008, 27, 202-210
Huynh, H. V.; Han, Y.; Jothibasu, R.; Yang, J. A. Organometallics 2009, 28, 5395-5404
Gusev, D. G. Organometallics 2009, 28, 6458-6461
Flack, H. D. Acta Crystallogr. 1983, A39, 876-881
Martín, M.; Gevert, O.; Werner, H. J. Chem. Soc., Dalton Trans. 1996, 2275-2283
Slugovc, C.; Mereiter, K.; Zobetz, E.; Schmid, R.; Kirchner, K. Organometallics 1996, 15, 5275-5277
Fürstner, A.; Ackermann, L.; Gabor, B.; Goddard, R.; Lehmann, C. W.; Mynott, R.; Stelzer, F.; Thiel, O. R. Chem. - Eur. J. 2001, 7, 3236-3253
Prühs, S.; Lehmann, C. W.; Fürstner, A. Organometallics 2004, 23, 280-287
Ledoux, N.; Allaert, B.; Pattyn, S.; Vander Mierde, H.; Vercaemst, C.; Verpoort, F. Chem. - Eur. J. 2006, 12, 4654-4661
Leuthäusser, S.; Schmidts, V.; Thiele, C. M.; Plenio, H. Chem. - Eur. J. 2008, 14, 5465-5481
Sauvage, X.; Zaragoza, G.; Demonceau, A.; Delaude, L. Adv. Synth. Catal. 2010, 352, 1934-1948
Speck, A. L. J. Appl. Crystallogr. 2003, 36, 7-13
For early examples, see: Bruce, M. I.; Swincer, A. G.; Wallis, R. C. J. Organomet. Chem. 1979, 171, C5-C8
Oro, L. A.; Ciriano, M. A.; Campo, M.; Foces-Foces, C.; Cano, F. H. J. Organomet. Chem. 1985, 289, 117-131
Mezzetti, A.; Consiglio, G.; Morandini, F. J. Organomet. Chem. 1992, 430, C15-C18
Bianchini, C.; Innocenti, P.; Peruzzini, M.; Romerosa, A.; Zanobini, F. Organometallics 1996, 15, 272-285
Pavlik, S.; Gemel, C.; Slugovc, C.; Mereiter, K.; Schmid, R.; Kirchner, K. J. Organomet. Chem. 2001, 617-618, 301-310
Pavlik, S.; Schmid, R.; Kirchner, K. Monatsh. Chem. 2004, 135, 1349-1357
Chiu, P. L.; Lee, H. M. Organometallics 2005, 24, 1692-1702
Solari, E.; Gauthier, S.; Scopelliti, R.; Severin, K. Organometallics 2009, 28, 4519-4526
Coe, B. J.; Glenwright, S. J. Coord. Chem. Rev. 2000, 203, 5-80
Anderson, K. M.; Orpen, A. G. Chem. Commun. 2001, 2682-2683
Tudose, A.; Demonceau, A.; Delaude, L. J. Organomet. Chem. 2006, 691, 5356-5365
Maj, A.; Delaude, L.; Demonceau, A.; Noels, A. F. J. Organomet. Chem. 2007, 692, 3048-3056
Sauvage, X.; Borguet, Y.; Zaragoza, G.; Demonceau, A.; Delaude, L. Adv. Synth. Catal. 2009, 351, 441-455
Delaude, L.; Sauvage, X.; Demonceau, A.; Wouters, J. Organometallics 2009, 28, 4056-4064
Ritter, T.; Hejl, A.; Wenzel, A. G.; Funk, T. W.; Grubbs, R. H. Organometallics 2006, 25, 5740-5745
Stewart, I. C.; Ung, T.; Pletnev, A. A.; Berlin, J. M.; Grubbs, R. H.; Schrodi, Y. Org. Lett. 2007, 9, 1589-1592
Clavier, H.; Nolan, S. P. Chem. - Eur. J. 2007, 13, 8029-8036
Bieniek, M.; Michrowska, A.; Usanov, D. L.; Grela, K. Chem. - Eur. J. 2008, 14, 806-818
For early examples, see: Katz, T. J.; Lee, S. J. J. Am. Chem. Soc. 1980, 102, 422-424
Foley, H. C.; Strubinger, L. M.; Targos, T. S.; Geoffroy, G. L. J. Am. Chem. Soc. 1983, 105, 3064-3073
Desbois, M.-H.; Astruc, D. New J. Chem. 1989, 13, 595-600
Hérisson, J.-L.; Chauvin, Y. Makromol. Chem. 1971, 141, 161-176
Katsumata, T.; Shiotsuki, M.; Sanda, F.; Sauvage, X.; Delaude, L.; Masuda, T. Macromol. Chem. Phys. 2009, 210, 1891-1902
APPEX II; Bruker AXS Inc.; Madison, WI, 2004.
Burla, M. C.; Caliandro, R.; Camalli, M.; Carrozzini, B.; Cascarano, G. L.; De Caro, L.; Giacovazzo, C.; Polidori, G.; Spagna, R. J. Appl. Crystallogr. 2005, 38, 381-388
Sheldrick, G. M. SHELX-97 (SHELXS 97 and SHELXL 97), Programs for Crystal Structure Analyses; University of Göttingen: Göttingen, Germany, 1998.
Sheldrick, G. M. SADABS, Programs for Scaling and Correction of Area Detection Data; University of Göttingen: Göttingen, Germany, 1996.

Name	Provider / Domaine	Expiration	Description
JSESSIONID	Oracle Corporation www.uliege.be	Session	General purpose platform session cookie, used by sites written in JSP. Usually used to maintain an anonymous user session by the server.
CookieScriptConsent	CookieScript .uliege.be	1 year	This cookie is used by Cookie-Script.com service to remember visitor cookie consent preferences. It is necessary for Cookie-Script.com cookie banner to work properly.

Name	Provider / Domaine	Expiration	Description
_pk_id	InnoCraft Ltd .uliege.be	1 year	Used to store a few details about the user such as the unique visitor ID
_pk_ses	InnoCraft Ltd .uliege.be	30 minutes	Short lived cookies used to temporarily store data for the visit
_pk_ref	InnoCraft Ltd .uliege.be	6 months	Used to store the attribution information, the referrer initially used to visit the website