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  • 1
    ISSN: 0009-2940
    Keywords: Methylenebisphosphanes ; Clusters ; Phosphinidene fragmentation ; Regioselectivity ; Phosphaalkene ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dehalogenation and Regioselective Phosphinidene Fragmentation of Unsymmetrically Substituted Methylenebisphosphanes RXP-CH2-PXR′ with Fe2(CO)9Reductive dehalogenation of the unsymmetrically substituted methylenebisphosphanes RXP-CH2-PR′X [X = Cl, Br; R = tBu, NEt2; R′ = 2,4,6-R”3C6H2 (R” = Me, tBu), NEt2, 2,6-iPr2C6-H3O, 2,6,4-tBu2MeC6H2O] with Fe2(CO)9 affords, depending on the reaction conditions employed, phosphido complexes [μ2-(RP-CH2-PR′)]Fe2(CO)6 (2) or phosphaalkene clusters (μ3-PR′)(η2,μ3-PRCH2)Fe3(CO)9(6) or [(μ-PR)(η2,μ3PR′CH2)]Fe3-(CO)9 (7), respectively, by regioselective phosphinidene fragmentation of the RP-CH2-PR′ skeletons. The unstable cluster compounds [μ3-PR′-CH2-PR)]Fe3(CO)9 (4) are formed as intermediate products. X-ray structural analysis of 6c (R = tBu; R′ = NEt2) reveals a flat butterfly (μ3-PR)Fe3 structure bridged by the phosphaalkene ligand tBuP = CH2 with a short P = C distance [177.2(4) pm].
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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