Farmer, Julian DMan, Wing YFox, Mark AYufit, Dmitri SHoward, Judith A KHill, AnthonyLow, Paul J2015-12-100022-328Xhttp://hdl.handle.net/1885/69326Reaction of RuHCl(CO)(PPh3)3 with aryl alkynes HCCC6H4R-4 [1: R = N(C6H4Me-4) 2 (a), OMe (b), Me (c), CO2Me (d), NO2 (e)] gives the five-coordinate vinyl complexes Ru(CHCHC6H 4R-4)Cl(CO)(PPh3)2 (2a-e). Reaction of 2a with excess PMe3 gives crystallographically characterised Ru{CHCHC 6H4N(C6H4Me-4)2-4}Cl(CO) (PMe3)3 (3a), whilst reaction of 2a-e with KTp affords Ru(CHCHC6H4R-4)(CO)(PPh3)Tp (4a-e) bearing the facially capping Tp- ligand. Electrochemical and spectroelectochemical properties of 4a-e are consistent with substantial redox activity associated with the vinyl ligand, and these properties have been satisfactorily modelled by DFT based calculations of electronic structure.Keywords: Aryl alkynes; Non-innocence; Pyrazolyl; Redox activity; Redox property; Vinyl; Vinyl complexes; Acetylene; Carbon dioxide; Chlorine compounds; Electronic structure; Ligands; Redox reactions; Ruthenium; Spectroelectrochemistry; Ruthenium compounds Redox non-innocence; Ruthenium; Spectroelectrochemistry; Vinyl201210.1016/j.jorganchem.2012.09.0012016-02-24