Abstract
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].
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