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  • Phosphorus ylides  (3)
  • Oxidative addition  (1)
  • 1
    Electronic Resource
    Electronic Resource
    Dreizentren-oxidative Addition von Phosphor-Yliden an Ru3(CO)12 (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 355-363 
    Details
    ISSN: 0009-2940
    Keywords: Ruthenium clusters ; Phosphorus ylides ; Oxidative addition ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three-Centre Oxidative Addition of Phosphorus Ylides to Ru3(CO)12Phosphorus ylides undergo oxidative addition to Ru3(CO)12 to yield a wide range of Ru3 clusters with triply bridging organic ligands derived from the ylides. Ph3P=CH2 forms HRu3(CO)9(μ31-Ph3P  -  CH  -  CO) (1) containing a phosphonio enolate. Ph3P=CH  -  CHO yields a product mixture containing the phosphonio enolate-bridged cluster and its PPh3 derivative 6, the phosphoniomethylidyne-bridged compound H2Ru3(CO)9(μ31-C  -  PPh3) (5), and the ketenylidene-bridged compound H2Ru3(CO)8(PPh3)(μ31-C  -  CO) (7). Thermal treatment converts the phosphonio enolate ligand (in 1) into the phosphoniomethylidyne ligand (in 5), and the latter into the ketenylidene ligand (in 7). With Ph3P=CH  -  C(O)Me and Ru3(CO)12 ortho1-metalated Ru3 derivatives 10, 11 of the phosphonio ketone R3P  -  C  -  C(O)Me are produced, and likewise with Ph3P=CH  -  COOEt the ortho1-metalated derivative 12 of the phosphonio ester R3P  -  C  -  CO2Et. Me3P=CH  -  COOtBu is oxidatively added to form HRu3(CO)9(μ31-Me3P  -  C  -  COOtBu) (13) bearing a phosphonio ester ligand.  -  The crystal structures of 6 and 13 are reported. The sequence of Ru3 clusters and the bonding modes of the μ3 ligands can be related to the surface reactions during Fischer-Tropsch catalysis.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19931260212
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  • 2
    Electronic Resource
    Electronic Resource
    Reaktivität von Phosphor-Ylid-Derivaten auf Ru31-Clustern: Umwandlungen durch Alkin-Insertion (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 365-371 
    Details
    ISSN: 0009-2940
    Keywords: Ruthenium clusters ; Phosphorus ylides ; Triply bridging organic ligands ; Alkyne insertion ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactivity of Derivatives of Phosphorus Ylides on Ru3 Clusters: Interconversions due to Alkyne InsertionThe Ru3 clusters with triply bridging organic ligands derived from phosphorus ylides undergo interconversions by insertion of alkynes. The phosphoniomethylidyne-bridged cluster H2Ru3(CO)9(μ31-C  -  PPh3) (1) inserts alkynes either into one Ru  -  H bond (HC=CSiMe3, EtC=CEt) forming μ21-vinyl-Ru3 complexes or into the Ru3-μ31-C unit (HC=CSiMe3, PhC=CPh) converting it into a μ31-allyl ligand, e.g. in Ru3(CO)8(PPh3)(μ31-Ph3P  -  C=CH=CSiMe3) (6). HC=CPh induces fragmentation of 1. The phosphonio enolate-bridged clusters HRu3(CO)9-(μ31-Ph3P  -  CH  -  CO) (2a) and HRu3(CO)8(PPh3)(μ31-Ph3P  -  CH  -  CO) (2b) insert alkynes (HC=CPh, PhC=CPh, HC=CSiMe3, EtC=CEt) into the Ru  -  H bond to form μ21-vinyl-bridged derivatives, e.g. Ru3(CO)8(μ31-Ph3P  -  CH  -  CO)(μ21-RC=CHR′) (9). In addition, the alkyne reactions of 2a induce cluster opening with concomitant CO and alkyne incorporation into the organic ligand and formation of an oxaruthenol-derived trinuclear complex 11, as proved by an X-ray structure determination of the PhC=CPh product 11b. For the cluster H2Ru3(CO)7(PPh3)(μ31-C6H4Ph2P  -  C(O)Me) (3) containing an ortho1-metalated phosphonio ketone ligand, only alkyne insertion into one or two Ru  -  H units is observed.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19931260213
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    Paper (German National Licenses)
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  • 3
    Electronic Resource
    Electronic Resource
    Rutheniumcluster-vermittelter Aufbau von Kohlenstoff-Ketten aus einem Phosphor-Ylid und Alkinen (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 373-377 
    Details
    ISSN: 0009-2940
    Keywords: Ruthenium clusters ; Phosphorus ylides ; Cluster fragmentation ; Alkyne coupling ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ruthenium cluster-Mediated Formation of Carbon Chains from a Phosphorus Ylide and AlkynesThe phosphorus ylide Me3P=CH  -  C(O)Ph induces fragmentation of Ru3(CO)12 with formation of the dinuclear complex Ru2(CO)7(μ21-HC_… CPh=CH  -  C(O)Ph) (1a) with a σ,π1-bound allyl ligand, together with its PMe3 derivative 1b. The latter inserts PhC=CPh into the Ru  -  C s̰ bond to yield two isomeric complexes Ru2(CO)5(PMe3)[μ1-CPh \documentclass{article}\pagestyle{empty}\begin{document}$ \underline \cdots $\end{document} CPh \documentclass{article}\pagestyle{empty}\begin{document}$ \underline \cdots $\end{document} CH  -  CPh=CH  -  C(O)Ph] (3a, b) with a (σ,π1-allyl,π1-olefin)1-coordinated six-carbon chain ligand. With HC=CPh 1b undergoes double insertion with formation of the complex Ru2(CO)4(PMe3)(μ1-CH=CPh=CH  -  CPh=CH  -  CPh=CH  -  C(O)Ph] (4) containing an eight-carbon chain ligand with (σ,π1-allyl,π1-olefin,π1-olefin) coordination. The structure of 3a (and thereby indirectly the constitution of 1 and 4) was proved by an X-ray structure determination.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19931260214
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