Reaktivität von Phosphor‐Ylid‐Derivaten auf Ru 3 1‐Clustern: Umwandlungen durch Alkin‐Insertion

Reactivity of Derivatives of Phosphorus Ylides on Ru 3 Clusters: Interconversions due to Alkyne Insertion The Ru 3 clusters with triply bridging organic ligands derived from phosphorus ylides undergo interconversions by insertion of alkynes. The phosphoniomethylidyne‐bridged cluster H 2 Ru 3 (CO) 9 (μ 3 1‐C — PPh 3 ) ( 1 ) inserts alkynes either into one Ru — H bond (HCCSiMe 3 , EtCCEt) forming μ 2 1‐vinyl‐Ru 3 complexes or into the Ru 3 ‐μ 3 1‐C unit (HCCSiMe 3 , PhCCPh) converting it into a μ 3 1‐allyl ligand, e.g. in Ru 3 (CO) 8 (PPh 3 )(μ 3 1‐Ph 3 P — CCHCSiMe 3 ) ( 6 ). HCCPh induces fragmentation of 1 . The phosphonio enolate‐bridged clusters HRu 3 (CO) 9 ‐(μ 3 1‐Ph 3 P — CH — CO) ( 2a ) and HRu 3 (CO) 8 (PPh 3 )(μ 3 1‐Ph 3 P — CH — CO) ( 2b ) insert alkynes (HCCPh, PhCCPh, HCCSiMe 3 , EtCCEt) into the Ru — H bond to form μ 2 1‐vinyl‐bridged derivatives, e.g. Ru 3 (CO) 8 (μ 3 1‐Ph 3 P — CH — CO)(μ 2 1‐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 H 2 Ru 3 (CO) 7 (PPh 3 )(μ 3 1‐C 6 H 4 Ph 2 P — C(O)Me) ( 3 ) containing an ortho 1‐metalated phosphonio ketone ligand, only alkyne insertion into one or two Ru — H units is observed.