ChemInformVolume 20, Issue 3 Preparative Organic Chemistry ChemInform Abstract: Bimetallic Activation in Homogeneous Catalysis: Palladium-Catalyzed Carbonylation of Tricarbonyl(chloroarene)chromium Complexes to the Corresponding Aldehydes, Esters, Amides, and α-Oxo Amides. R. MUTIN, R. MUTIN Inst. Rech. Catal., Univ. Claude Bernard, CNRS, 69626 Villeurbanne, FranceSearch for more papers by this authorC. LUCAS, C. LUCAS Inst. Rech. Catal., Univ. Claude Bernard, CNRS, 69626 Villeurbanne, FranceSearch for more papers by this authorJ. THIVOLLE-CAZAT, J. THIVOLLE-CAZAT Inst. Rech. Catal., Univ. Claude Bernard, CNRS, 69626 Villeurbanne, FranceSearch for more papers by this authorV. DUFAUD, V. DUFAUD Inst. Rech. Catal., Univ. Claude Bernard, CNRS, 69626 Villeurbanne, FranceSearch for more papers by this authorF. DANY, F. DANY Inst. Rech. Catal., Univ. Claude Bernard, CNRS, 69626 Villeurbanne, FranceSearch for more papers by this authorJ. M. BASSET, J. M. BASSET Inst. Rech. Catal., Univ. Claude Bernard, CNRS, 69626 Villeurbanne, FranceSearch for more papers by this author R. MUTIN, R. MUTIN Inst. Rech. Catal., Univ. Claude Bernard, CNRS, 69626 Villeurbanne, FranceSearch for more papers by this authorC. LUCAS, C. LUCAS Inst. Rech. Catal., Univ. Claude Bernard, CNRS, 69626 Villeurbanne, FranceSearch for more papers by this authorJ. THIVOLLE-CAZAT, J. THIVOLLE-CAZAT Inst. Rech. Catal., Univ. Claude Bernard, CNRS, 69626 Villeurbanne, FranceSearch for more papers by this authorV. DUFAUD, V. DUFAUD Inst. Rech. Catal., Univ. Claude Bernard, CNRS, 69626 Villeurbanne, FranceSearch for more papers by this authorF. DANY, F. DANY Inst. Rech. Catal., Univ. Claude Bernard, CNRS, 69626 Villeurbanne, FranceSearch for more papers by this authorJ. M. BASSET, J. M. BASSET Inst. Rech. Catal., Univ. Claude Bernard, CNRS, 69626 Villeurbanne, FranceSearch for more papers by this author First published: January 17, 1989 https://doi.org/10.1002/chin.198903113Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat No abstract is available for this article. References R. MUTIN, C. LUCAS, J. THIVOLLE-CAZAT, V. DUFAUD, F. DANY, J. M. BASSET, Bimetallic Activation in Homogeneous Catalysis: Palladium-Catalyzed Carbonylation of Tricarbonyl(chloroarene)chromium Complexes to the Corresponding Aldehydes, Esters, Amides, and α-Oxo Amides., J. Chem. Soc., Chem. Commun., 1988, 896. DOI: 10.1039/c39880000896; 10.1039/C39880000896 Web of Science®Google Scholar Volume20, Issue3January 17, 1989 ReferencesRelatedInformation

The syntheses of a number of cyclopentadienylcarbene iron half sandwich complexes are described. In addition to their spectroscopic characterization an X-ray crystal structure analysis is provided. The complexes prepared include chromium, molybdenum, and tungsten carbene complexes. The dicarbonyliron unit is substituted by benzyl, butyl or trimethylsilylmethyl groups. In two cases tetrametallic dimeric complexes connected by a propyl chain are presented. The reaction of the formylcyclopentadienyliron complex with a chromium carbene complex provided a vinylogous representative. Cyclic voltammetry was performed, and the data obtained are discussed in comparison to similar ferrocene based complexes.

R. Mutin, C. Lucas, J. Thivolle-Cazat, V. Dufaud, F. Dany and J. M. Basset, J. Chem. Soc., Chem. Commun., 1988, 896 DOI: 10.1039/C39880000896

The new chiral clusters Rh4(CO)10[(—)-DIOP] 1 and Rh6(CO)10[XXX] (XXX = (+)- or (—)-DIOP 2, (S,S)-chiraphos 3, (S)-peap 4) have been synthesized by ligand exchange from the parent clusters Rh4(CO)12 5 and Rh6-(CO)16 6. Assymetric hydrogenation of the methylester of Z-α-acetamido cinnamic acid has been carried out with the clusters 1–6, either alone or associated with n equivalents of (+)- or (—)-DIOP. Only for XXX = (+)- or (—)-DIOP an enantioselectivity is observed which depends mainly on the overall ratio DIOP/Rh. A maximum of activity and enantioselectivity (e.e. ≌ 60% R (—)) is achieved regardless of the precursor complex 1, 2, 5 or 6, provided the ratio (—)-DIOP/Rh is equal to or higher than unity. Spectroscopic studies indicate that the cluster 1 associated with 3 equivalents of (—)-DIOP undergoes a series of transformations which lead to Rh4(CO)8[(—)-DIOP]2 7 and [Rh(CO)[(—)-DIOP]]2 (μ-CO)2 8. 8 is the most abundant component, which oxidatively adds H2 reversibly at room temperature to give HRh(CO)2[(—)-DIOP] and related complexes. This mononuclear complex is the catalytically active component. Apparently the oxidative addition of H2 does not occur on the clusters 1, 2, 3, 4 but only on the zero-valent rhodium dimer 8 for which the P/Rh ratio is equal to unity.

Rh6(CO)10[(-)DIOP]3 has been isolated after ligand exchange between Rh6(CO)16 and DIOP. The molecular cluster is an efficient catalyst for asymmetric reduction of various prochiral olefins; optical yields up to 47% have been achieved; the results are compared with those obtained with mononuclear rhodium (I) complexes.

Variable temperature 13C and 31P NMR studies on Rh6(CO)12[P(OPh)3]4 show that the solid state structure is maintained in solution from −80 to 60°C. Above 60°C there is a fluxional motion of some of the carbonyls between triply-bridging and edge-bridging positions. The onset of this fluxionality parallels the appearance of catalytic activity in hydrogenation of cyclohexene.

Variable temperature 13C and 31P NMR studies on Rh6(CO)12[P(OPh)3]4 show that the solid state structure is maintained in solution from −80 to 60°C. Above 60°C there is a fluxional motion of some of the carbonyls between triply-bridging and edge-bridging positions. The onset of this fluxionality parallels the appearance of catalytic activity in hydrogenation of cyclohexene.

Metathesis of olefinic amines has been studied with two purposes: (i) to try to carry out at a stoichiometric (or slightly catalytic) level metathesis of olefinic amines to obtain telechelic compounds; (ii) to try to find which parameters play a role in the catalytic process.

Chemischer InformationsdienstVolume 9, Issue 4 Preparative Organic Chemistry ChemInform Abstract: LIGAND EFFECTS IN METATHESIS OF OLEFINS WITH ZEROVALENT COMPLEXES OF TUNGSTEN J. L. BILHOU, J. L. BILHOUSearch for more papers by this authorR. MUTIN, R. MUTINSearch for more papers by this authorM. LECONTE, M. LECONTESearch for more papers by this authorJ. M. BASSET, J. M. BASSETSearch for more papers by this author J. L. BILHOU, J. L. BILHOUSearch for more papers by this authorR. MUTIN, R. MUTINSearch for more papers by this authorM. LECONTE, M. LECONTESearch for more papers by this authorJ. M. BASSET, J. M. BASSETSearch for more papers by this author First published: January 24, 1978 https://doi.org/10.1002/chin.197804113AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume9, Issue4January 24, 1978 RelatedInformation

AbstractZur Klärung des Mechanismus der geometrischen Isomerisierung von cis‐ bzw. trans‐ Penten‐(2) wird die Metathese beider Verbindungen in Gegenwart von W‐Komplexen Wie Z‐ B‐ W(C0)5PPh3‐Äthyl‐Al‐dichlorid durchgeführt.

Whereas metathesis of olefins with primary or tertiary amino groups is ineffective with conventional catalysts, metathesis of olefins with quarternary ammonium groups results in α–ω bifunctional olefins.

Chemischer InformationsdienstVolume 7, Issue 9 Preparative Organic Chemistry ChemInform Abstract: STERIC ENVIRONMENT OF THE ACTIVE CENTER IN METHATHESIS OF OLEFINS J. M. BASSET, J. M. BASSETSearch for more papers by this authorJ. L. BILHOU, J. L. BILHOUSearch for more papers by this authorR. MUTIN, R. MUTINSearch for more papers by this authorA. THEOLIER, A. THEOLIERSearch for more papers by this author J. M. BASSET, J. M. BASSETSearch for more papers by this authorJ. L. BILHOU, J. L. BILHOUSearch for more papers by this authorR. MUTIN, R. MUTINSearch for more papers by this authorA. THEOLIER, A. THEOLIERSearch for more papers by this author First published: March 2, 1976 https://doi.org/10.1002/chin.197609071Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume7, Issue9March 2, 1976 RelatedInformation

Kinetic studies of metathesis of ω-arylolefins have been performed with two types of catalytic systems derived from molybdenum and tungsten. The effect of the structure of these olefins on their reactivity has been studied in terms of three variables: length of the chain between the aromatic ring and the double bond, substituent effects at the double bond, and substituent effects on the aromatic ring. The results are discussed in terms of a “one carbene” exchange mechanism, on the basis of steric and electronic effects of the olefin.

A model is proposed which accounts for both the observed metathesis and the cis-trans isomerisation, as measured by the relative amounts of the various olefins produced at low conversion from the reaction of cis-pent-2-ene on a tungsten catalyst.

Kinetic studies of metathesis of ω-arylolefins have been performed with two types of catalytic systems derived from molybdenum and tungsten. The effect of the structure of these olefins on their reactivity has been studied in terms of three variables: length of the chain between the aromatic ring and the double bond, substituent effects at the double bond, and substituent effects on the aromatic ring. The results are discussed in terms of a “one carbene” exchange mechanism, on the basis of steric and electronic effects of the olefin.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSteric environment of the active center in methathesis of olefinsJ. M. Basset, J. L. Bilhou, R. Mutin, and A. TheolierCite this: J. Am. Chem. Soc. 1975, 97, 25, 7376–7377Publication Date (Print):December 1, 1975Publication History Published online1 May 2002Published inissue 1 December 1975https://pubs.acs.org/doi/10.1021/ja00858a029https://doi.org/10.1021/ja00858a029research-articleACS PublicationsRequest reuse permissionsArticle Views118Altmetric-Citations45LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts