title: Metalloligands containing aminofulvene-aldiminate (AFA) ligands and their bimetallic complexes.
abstract: A simple and convenient route to η(5)-coordinated Ru and Rh aminofulvene-aldiminate (AFA) complexes is described. The metalloligands [Cp*Ru{η(5)-(Ph(2)AFAH)}][BF(4)] (3), [Cp*Ru{η(5)-(benzyl(2)AFAH)}][OTf] (7), [Cp*Rh{η(5)-(Cy(2)AFA)H}][BF(4)](2) (8) and [Cp*Rh{η(5)-(Cy(2)AFA)}][BF(4)] (9) have been synthesised and characterised. The basicity of 9 has been found to be significantly less than its neutral analogue and thus eliminates the need for a deprotonation step to ligate to a second metal in the κ(2)-N,N'-coordination mode. The reaction of 9 with a palladium precursor provides a mixed-metal complex [Cp*Rh(η(5)/κ(2)-Cy(2)AFA)PdCl(2)][BF(4)] (12). Cyclic voltammetry studies of the Ph(2)AFAH ligand shows an irreversible one electron oxidation peak at +1.0 V (vs. Fc/Fc(+)). Complex 3 shows an irreversible oxidation at +1.5 V and a reduction peak at -1.0 V. The oxidation of 3 occurs on the AFA ligand backbone whereas the structurally analogous neutral 1,2-bis(imidoyl)pentamethyl-ruthenocene shows reversible oxidation at the Ru center.
authors.affiliation: School of Chemistry, University of Edinburgh, The King's Buildings, West Mains Road, Edinburgh, EH9 3JJ, UK. Philip.Bailey@ed.ac.uk
authors.forename: Philip J
authors.initials: PJ
authors.lastname: Bailey
authors.forename: Mahmudur
authors.initials: M
authors.lastname: Rahman
authors.forename: Simon
authors.initials: S
authors.lastname: Parsons
authors.forename: Muhammad R
authors.initials: MR
authors.lastname: Azhar
authors.forename: Fraser J
authors.initials: FJ
authors.lastname: White
mesh_terms: D003517:Cyclopentanes / Q000737:chemistry*; D007097:Imines / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D012211:Rhenium / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*
chemical_list: D003517:Cyclopentanes; D007097:Imines; D008024:Ligands; D009942:Organometallic Compounds; C017332:fulvene; D012211:Rhenium; D012428:Ruthenium