Synthesis, reactivity and catalytic properties of the allenylidene [Ru(C=C=CPh2)Cp(PTA)(PPh3)](CF3SO3) (PTA=1,3,5-triaza-7-phosphaadamantane)

The reactivity of [RuCpCl(PTA)(PPh3)] with HC CPh and HC CC(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-kappa S)(PTA)(PPh3)](CF3SO3) (1) was obtained by reaction of [RuCpCl(PTA)(PPh3)] with Ag(CF3SO3) in DMSO. Reaction of [RuCpCl(PTA)(PPh3)] with HC CC(OH) PPh2 provided the Ruthenium(II) diphenyl-allenylidene complex [Ru(C=C=CPh2)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, O-2, 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-butanedioldivinyl- ether, ethoxyethene and 1-methoxycyclohexa-1,3-diene (c) 2013 Elsevier B.V. All rights reserved.