Synthesis, reactivity and catalytic properties of the allenylidene [Ru(CCCPh2)Cp(PTA)(PPh3)](CF3SO3) (PTA = 1,3,5-triaza-7-phosphaadamantane)

• Water soluble organometallic complexes.
• Homogeneous catalysis in water.
• Allenylidene complexes in catalysis.
• Chemistry and catalysis of organometallic ruthenium complexes.
• Metal complex homogeneous catalytic trans-etherification in water in mild conditions.

The reactivity of [RuCpCl(PTA)(PPh3)] with HCCPh and HCCC(OH)PPh2 has been studied. The reaction with the phenylacetylene did not provide the desired vinylidene ruthenium complex but as a collateral result the complex [RuCp(DMSO-κS)(PTA)(PPh3)](CF3SO3) (1) was obtained by reaction of [RuCpCl(PTA)(PPh3)] with Ag(CF3SO3) in DMSO. Reaction of [RuCpCl(PTA)(PPh3)] with HCCC(OH)PPh2 provided the Ruthenium(II) diphenyl-allenylidene complex [Ru(CCCPh2)Cp(PTA)(PPh3)](CF3SO3) (2) that was characterized by NMR, IR spectroscopy and elemental analysis. The chemistry of the new diphenyl-allenylidene ruthenium complex has been studied towards a variety of small molecules such as water, O2, n-propylamine, cyclohexylamine and ethanethiol. From the reaction of 2 with the amines and thiol, two isomers are obtained respectively but only one of them could be isolated and characterized. The allenylidene complex was found to be a useful catalyst for the trans-etherification of 1,4-butanediol-divinyl-ether, ethoxyethene and 1-methoxycyclohexa-1,3-diene

The ruthenium(II) diphenyl-allenylidene complex [Ru(CCCPh2)Cp(PTA)(PPh3)](CF3SO3) was synthesized and characterized. Its chemical reactivity towards a variety of small molecules has been studied, which showed it to be a useful catalyst for the trans-etherification of diol-divinyl-ethers.Figure optionsDownload as PowerPoint slide