title: Ruthenium bipyridyl compounds with two terminal alkynyl ligands.
abstract: Compounds of the form Ru(X2bipy)(PPh3)2(-C triple bond CC6H4NO2-p)2(X2bipy = 4,4'-X(2)-2,2'-bipyridine, X = Me 3a, Br 3b, I 3c) have been synthesised from the mono-alkynyl precursors Ru(X2bipy)(PPh3)2(-C triple bond CC6H4NO2-p)Cl (X = Me 2a, Br 2b, I 2c); the former are the first ruthenium bis-alkynyl compounds that also contain a bipyridyl ligand. Spectroelectrochemical investigation of 3a shows that the metal is readily oxidised to form the ruthenium(III) compound 3a+, and will also undergo a single-electron reduction at each nitro group to form 3a2-. ESR and UV/visible spectra of these redox congeners are presented. We also report the synthesis of [Ru(Me2bipy)(PPh3)2(-C triple bond CBut)(N triple bond N)][PF6] during the attempted synthesis of Ru(Me2bipy)(PPh3)2(-C triple bond CBut)2, and report its X-ray crystal structure and IR spectrum. X-Ray crystal structures of 3b and 3c(as two different solvates) are presented, and the nature of the intermolecular interactions seen therein is discussed. Z-Scan measurements on Ru(Me2bipy)(PPh3)2(-C triple bond CR)Cl (R = C6H4NO2-p2a, But, Ph, C6H4Me) are also reported, and show that Ru(Me2bipy)(PPh3)2(-C triple bond CR)Cl (R = C6H4NO2-p2a, Ph) exhibit moderate third-order non-linearities.
authors.affiliation: School of Chemistry, University of Bristol, Bristol, UKBS8 1TS. chcja@bris.ac.uk.
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Adams
authors.forename: Lucy E
authors.initials: LE
authors.lastname: Bowen
authors.forename: Mark G
authors.initials: MG
authors.lastname: Humphrey
authors.forename: Joseph P L
authors.initials: JP
authors.lastname: Morrall
authors.forename: Marek
authors.initials: M
authors.lastname: Samoc
authors.forename: Lesley J
authors.initials: LJ
authors.lastname: Yellowlees