Reaktivität von Phosphor‐Ylid‐Derivaten auf Ru31‐Clustern: Umwandlungen durch Alkin‐Insertion

Abstract

Reactivity of Derivatives of Phosphorus Ylides on Ru3 Clusters: Interconversions due to Alkyne InsertionThe Ru3 clusters with triply bridging organic ligands derived from phosphorus ylides undergo interconversions by insertion of alkynes. The phosphoniomethylidyne‐bridged cluster H2Ru3(CO)9(μ31‐C — PPh3) (1) inserts alkynes either into one Ru — H bond (HCCSiMe3, EtCCEt) forming μ21‐vinyl‐Ru3 complexes or into the Ru3‐μ31‐C unit (HCCSiMe3, PhCCPh) converting it into a μ31‐allyl ligand, e.g. in Ru3(CO)8(PPh3)(μ31‐Ph3P — CCHCSiMe3) (6). HCCPh induces fragmentation of 1. The phosphonio enolate‐bridged clusters HRu3(CO)9‐(μ31‐Ph3P — CH — CO) (2a) and HRu3(CO)8(PPh3)(μ31‐Ph3P — CH — CO) (2b) insert alkynes (HCCPh, PhCCPh, HCCSiMe3, EtCCEt) into the Ru — H bond to form μ21‐vinyl‐bridged derivatives, e.g. Ru3(CO)8(μ31‐Ph3P — CH — CO)(μ21‐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 H2Ru3(CO)7(PPh3)(μ31‐C6H4Ph2P — C(O)Me) (3) containing an ortho1‐metalated phosphonio ketone ligand, only alkyne insertion into one or two Ru — H units is observed.