Dreizentren-oxidative Addition von Phosphor-Yliden an Ru3(CO)12

Three-Centre Oxidative Addition of Phosphorus Ylides to Ru₃(CO)₁₂ Phosphorus 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.