Cyclopentadienyl-ruthenium and -osmium chemistry. XXIII. Synthesis and reactions of some hydrido complexes containing ruthenium or osmium, and related chemistry

Abstract

The hydrido complexes HM(PPh₃)₂(η-C₅H₅) (M = Ru, O_s), HFe(dppe)(η-C₅H₅), HRu(L₂)(η-C₅H₅) (L₂ = dppe, dppm or dpae), HRu(AsPh₃),(η-C₅H₅)_, HRu(L)(PPh₃)(η-C₅H₅) [L = CNBu^t, P(OPh)₃] have been obtained from reactions between the analogous chloro complexes and NaOMe/MeOH; RuCI[P(OPh)₃]₂(η-C₅H₅) affords the cyclometallated

Ru[(C₆H₄O)P(OPh)₃)₂][P(Oph)₃]η-C₅H₅)

under these conditions. Reactions between HRu(PPh₃)₂(η C₅H₅) and HX or CHX₃ (X = Cl, Br, I) afford the corresponding halo complexes RuX(PPh₃)₂(η-C₅H₅); CS₂ reacts with HRuL₂(η-C₅H₅) (L = PPh₃, L₂ = dppe) to give the corresponding dithioformato derivatives. Ligand-exchange reactions of HRu(PPh₃)₂(η -C₅H₅) with CO or dppe proceed with difficulty at temperatures of c. 150-200ºC in an autoclave.