Le couplage alkylidyne-alcyne a lieu par reaction de H 3 Ru 3 (μ 3 -CX)(CO) 9 ou HRu 3 (μ-CX)(CO) 10 avec les alcynes formant des agregats dimetalloallyliques HRu 3 (μ 3 -η 3 -XCCRCR)(CO) 9

The heterometallic cluster complex CpWOs3(CO)9(μ-O)(μ-CCH2Tol), previously prepared by pyrolysis of the planar μ3-η2-acyl complex CpWOs3(CO)11[μ3-η2-OCCH2Tol], crystallizes in the centrosymmetric triclinic space group P1 with a 9.7041(25), b 9.7829(27), c 14.5992(39) Å, α 108.106(22), β 93.805(21), γ 94.565(22)°, V 1307.1(6) Å3 D(calcd) 3.06 g cm-3 for Z = 2 and mol. wt. 1204.8. Single-crystal X-ray diffraction data (Mo-Kα, 2θ 4.5–45.0°) were collected on a Syntex P21 automated four-circle diffractometer and the structure was refined to R 3.9% for all 3438 data (R 3.3% for those 3101 data with F0 > 3σ(|F0|). The molecule contains a tetrahedral WOs3 core associated with 60 valence electrons. The μ3-η2-acyl fragment of the precursor has undergone scission, leading to separate μ-oxo and μ3-CCH2Tol moieties. The μ-oxo ligand is linked by a double bond to tungsten (W=O 1.812(7) Å) and via a single donor bond to Os(1) (Os(1)← : O 2.169(8) Å, with ∠WOOs(1) 83.46(31)°. The μ-alkylidyne ligand is linked to a WOs2 face, with WC 2.030(12), Os(1)C 2.291(12) and Os(2)C 2.100(10) Å. The O(oxo)⋯C(alkylidyne) separation is now 3.15 Å and is clearly non-bonding.

AbstractErhitzen des Clusters (I) führt zur Spaltung der Acy ‐C‐O‐Bindung unter Bildung des Oxo‐Alkylidin‐ Komplexes (II), dessen Struktur (PT mit Z=2) röntgendiffraktometrisch bestimmt wird.

Substitution on (μ-H)3Ru3(μ3-CX)(CO)9 (X=OMe, Me, Cl, Ph) by triphenylarsine proceeds sequentially to (μ-H)3Ru3(μ3-CX)(CO)9−n(AsPh3)n (n = 1, 2, 3). A single-crystal X-ray crystallographic study of (μ-H)3Ru3(μ3-CPh)(CO)7(AsPh3)2 has been performed. This complex crystallizes in the centrosymmetric monoclinic space group C2/c [No. 15] with a 36.746(19), b 12.743(6), c 22.802(11) Å, β 108.60(4)°, V 10119 Å3 and Z = 8. Data for 2θ 4.0–35.0° (Mo-Kα were collected on a Syntex P21 automated four-circle diffractometer and the structure was refined to Rf 7.2% for all 3208 reflections (Rf 5.4% for those 2523 reflections with |Fo| > 6σ(|Fo|)). The crystal structure establishes axial coordination for the triphenylarsine ligands on different metal atoms. The rate of CO dissociation from (μ-H)3Ru3(μ3-CX)(CO)9 is found to depend upon X in the order: X = OMe (36) ⇌ > Me (3.2) > Cl (2.3) > Ph (1) at 298 K. The labilizing effect of the methoxy substituent is attributed to stabilization of the transition state by π-donation to the Ru3C core.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAlkylidyne-alkyne coupling on triruthenium clusters. A potential model for Fischer-Tropsch chain growthLawrence R. Beanan, Zuraidah Abdul Rahman, and Jerome B. KeisterCite this: Organometallics 1983, 2, 8, 1062–1064Publication Date (Print):August 1, 1983Publication History Published online1 May 2002Published inissue 1 August 1983https://pubs.acs.org/doi/10.1021/om50002a029https://doi.org/10.1021/om50002a029research-articleACS PublicationsRequest reuse permissionsArticle Views90Altmetric-Citations31LEARN 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-AlertscloseSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSynthesis of cyclohexadiene complexes of (methylidyne)triruthenium clusters. The crystal structure of (.mu.-H)Ru3(.mu.3-COMe)(CO)8(1,3-C6H8) and a redetermination of the structure of (.mu.-H)Ru3(.mu.-COMe)(CO)10Melvyn Rowen Churchill, Lawrence R. Beanan, Harvey J. Wasserman, Clifford Bueno, Zuraidah Abdul Rahman, and Jerome B. KeisterCite this: Organometallics 1983, 2, 9, 1179–1186Publication Date (Print):September 1, 1983Publication History Published online1 May 2002Published inissue 1 September 1983https://pubs.acs.org/doi/10.1021/om50003a019https://doi.org/10.1021/om50003a019research-articleACS PublicationsRequest reuse permissionsArticle Views76Altmetric-Citations24LEARN 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-AlertscloseSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts