The carbonyl hydrido complex RuHCl(CO)(PPh₃)₃ reacts with diynes HC₂RC₂H (R = p-C₆H₄, p-C₆H₄-C₆H₄) by insertion to give the five-coordinate vinyl ruthenium dimeric compounds [RuCl(CO) (PPh₃)₂]μ-CH=CH-R-CH=CH) in nearly quantitative yields. Additions of 3,5-dimethylphenylisocyanide (CNC₈H₉) or 4-phenyl pyridine ligand to the alkenyl complexes produce the six-coordinate complexes (C₈H₉NC)Ru(CO)Cl (PPh₃)₂ μ-CH=CH-R-CH=CH)Ru(CO)Cl(PPh3)2 (CNC₈H₉), (C₆H₅-C₆H₄N)Ru(CO)Cl(PPh₃) ₂μ-CH=CH-R-CH=CH)Ru(CO)Cl(PPh₃)₂ (NC₅H₄-C₆H₅). This reaction was applied to the synthesis of conjugated organometallic metal vinyl linkage containing oligomers [Ru(CO)Cl(PPh₃)₂(μ-CH=CH-R-CH=CH)Ru(CO) Cl(PPh₃)₂(μ-L)]n (L = 2,3,5,6-tetramethylphenyldiisocyanide, 4,4-bipyridine). ⁺...[ Read more ]

The carbonyl hydrido complex RuHCl(CO)(PPh₃)₃ reacts with diynes HC₂RC₂H (R = p-C₆H₄, p-C₆H₄-C₆H₄) by insertion to give the five-coordinate vinyl ruthenium dimeric compounds [RuCl(CO) (PPh₃)₂]μ-CH=CH-R-CH=CH) in nearly quantitative yields. Additions of 3,5-dimethylphenylisocyanide (CNC₈H₉) or 4-phenyl pyridine ligand to the alkenyl complexes produce the six-coordinate complexes (C₈H₉NC)Ru(CO)Cl (PPh₃)₂ μ-CH=CH-R-CH=CH)Ru(CO)Cl(PPh3)2 (CNC₈H₉), (C₆H₅-C₆H₄N)Ru(CO)Cl(PPh₃) ₂μ-CH=CH-R-CH=CH)Ru(CO)Cl(PPh₃)₂ (NC₅H₄-C₆H₅). This reaction was applied to the synthesis of conjugated organometallic metal vinyl linkage containing oligomers [Ru(CO)Cl(PPh₃)₂(μ-CH=CH-R-CH=CH)Ru(CO) Cl(PPh₃)₂(μ-L)]n (L = 2,3,5,6-tetramethylphenyldiisocyanide, 4,4-bipyridine).

Reactions between [Ru(THF)(PPh3)2(Cp)]⁺ and diynes gave further examples of dinuclear vinylidene ruthenium complexes [Ru]=C=CH-R-CH=C=[Ru] {[Ru] = Ru(PPh₃)₂(Cp)⁺, R = p-C₆H₄, p-C₆H₄- C₆H₄}. Subsequent deprotonation of vinylidene complexes by NaOMe produced corresponding acetylide dinuclear complexes.

A new synthetic route to compounds with "naked" C₅ bridging two metal centers is reported. Reaction of 2 equivalents of [Ru(PPh₃)₂(Cp)Cl] with HC₂CH(OH)C₂H, NaPF₆ and AgBF₄ leads to dinuclear cationic C₅-H complex [Cp(PPh₃)₂Ru=C=C-CH=C=C=Ru(PPh3)2 Cp][PF₆ after treatment with alumina. The cationic C₅-H complex could be converted into the corresponding neutral C₅ complex Cp(PPh₃)₂Ru≡C-C≡C-C[identical to][identical to] C-Ru(PPh₃)₂Cp by treatment with KO^t8u.

The monohydrido complex RuHCl(CO)(PPh₃)₃ reacts with HC≡CC(OH)R^lR² to give the hydroxyvinyl compounds RuCl((E)-CH≡CHC(OH)R^lR²} (CO)(PPh₃)₂ (R¹ = R² = H; R¹= R² = Me; R¹=Ph, R² = Me; R¹ = Me, R² = Et), which by reaction with HBF₄ afford [RuCl(=CHCH=CR^lR²)(CO)(PPh₃)₂] [BF₄] (R¹ = R² =Me; R¹ = Ph, R² = Me). Treatment of hydroxyvinyl. compounds in CH₂ Cl₂ with alumina affords corresponding dehydrated compounds RuCl(-CH=CH-CR'= CH2)(CO)(PPh₃)₂ (R' = Ph, Me). The hydroxyvinyl and butadienyl complexes react with 4-phenylpyridine to give corresponding six-coordinate complexes.