title: Alkene isomerisation catalysed by a ruthenium PNN pincer complex.
abstract: The [Ru(CO)H(PNN)] pincer complex based on a dearomatised PNN ligand (PNN: 2-di-tert-butylphosphinomethyl-6-diethylaminomethylpyridine) was examined for its ability to isomerise alkenes. The isomerisation reaction proceeded under mild conditions after activation of the complex with alcohols. Variable-temperature (VT) NMR experiments to investigate the role of the alcohol in the mechanism lend credence to the hypothesis that the first step involves the formation of a rearomatised alkoxide complex. In this complex, the hemilabile diethylamino side-arm can dissociate, allowing alkene binding cis to the hydride, enabling insertion of the alkene into the metal-hydride bond, whereas in the parent complex only trans binding is possible. During this study, a new uncommon Ru(0) coordination complex was also characterised. The scope of the alkene isomerisation reaction was examined.
authors.affiliation: Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen (The Netherlands), Fax: (+31) 50-3634296.
authors.forename: Sébastien
authors.initials: S
authors.lastname: Perdriau
authors.forename: Mu-Chieh
authors.initials: MC
authors.lastname: Chang
authors.forename: Edwin
authors.initials: E
authors.lastname: Otten
authors.forename: Hero J
authors.initials: HJ
authors.lastname: Heeres
authors.forename: Johannes G
authors.initials: JG
authors.lastname: de Vries
keywords: alcohols; alkene; isomerisation; pincer complex; ruthenium