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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 1111-1118 
    ISSN: 0009-2940
    Keywords: Aldehyde reactions ; Ruthenium clusters ; Oxidative addition ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oxidative Addition of Aldehydes and Schiff Bases to Ru3(CO)12Aldehydes show a wide variation of their reactive behaviour towards Ru3(CO)12. Aliphatic and simple aromatic aldehydes form simple oxidative addition products Ru3(CO)10(μ-H)(μ-RC = O) (1) either not at all or in low yields as impure compounds, while under forcing conditions dinuclear ruthenium μ-carboxylate complexes or the hydride H2Ru4(CO)13 are formed. Electron-rich aldehydes give good yields of cluster type 1 (R = p-MeOC6H4, p-Me2NC6H4, ferrocenyl). Schiff bases behave similarly, their oxidative addition products being Ru3(CO)10(μ-H)(μ-RC = NR′) (10, R = C6H5, p-MeOC6H4, p-Me2NC6H4, R′ = C6H5, p-MeC6H4). Of the ortho-substituted benzaldehydes, the methoxy compound produces clusters 6 and 7 resulting from aldehyde oxidative addition and aromatic ortho metalation. Salicylaldehyde and its p-tolylimine give the compounds Ru3(CO)8(μ-η2-OC6H4CH = X)2 (9, 11, X = O, NC6H4Me) with a bridging phenolate and a terminally bound aldehydic O or Schiff base NR function. 3-Pyridinecarbaldehyde reacts quickly with Ru3(CO)12 to give products 8 derived from pyridine CH rather than aldehyde CH oxidative addition. The crystal structures of 9 and 11 were determined.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 355-363 
    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
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