Ferrocenylphosphine derivatives of iron and ruthenium cluster carbonyls

The substitution reactions of Fe₃ (CO)₁₂ and Ru₃(CO)₁₂ with the ferrocenylphosphines PBuPhFc , PPh₂Fc , PPhFc₂, PFc₃ and Fe(C₅H₄)₂PPh were carried by initiation with the diphenyl-ketyl radical anion, or using photochemical or thermal conditions. The products Fe(CO)₄L (L=PBuPhFc, PPh₂Fc, PPhFc₂ and PFc₃); Fe₃(CO)₁₁ L (L=PBuPhFc and PPh₂Fc); Fe₃(CO)₁₀L₂, (L=PBuPhFc), Ru(CO)₄(PFc₃), Ru₃(CO)₁₁L (L=PPh₂Fc, PPhFc₂, PFc₃ and Fe(C₅H₄)₂2PPh); Ru₃ (CO)₁₀L₂ (L=PPh₂Fc, PPhFc₂, PFc₃ and Fe(C₅H₄)₂PPh), and Ru₃ (CO)₉L₃ (L=PPh₂Fc and PPhFc₂) were obtained in moderate to high yields with the exception of Ru(CO)₄(PFc₃) which was obtained in a very low yield and characterized by X-ray crystallographic analysis. The best method for the substitution reactions was found to be induction with the diphenylketyl radical anion. Pyrolytic reactions of three of the trimetallic ruthenium derivatives produced high to moderate yields of compounds with interesting spectroscopic data. A structure (XXXI) is proposed for the product obtained from the pyrolysis of Ru₃(CO)₁₀(PPh₂Fc)₂. It contains a ferrocene molecule bridging two metal atoms, a fluxional benzyne ring associated with all three metal atoms, and both doubly and triply bridging phosphido and phosphinidene ligands, respectively. [See Thesis for Diagram]Science, Faculty ofChemistry, Department ofGraduat