Organometallic Macrocycle Chemistry .2. Synthesis of Organometallic (trithiacyclononane)ruthenium(ii) Complexes

The reactions of 1,4,7-trithiacyclononane (9-S3) with the coordinatively unsaturated-sigma-vinyl complexes [Ru(CH=CHR)Cl(CO)PPh3)2] (R = H, C4H9, C6H4Me-4) proceed with loss of a chloride and a phosphine ligand from the coordination sphere to provide the salts [Ru-(CR=CHR)(CO)(PPh3)(9-S3)]Cl (isolated as AsF6- salts) in high yield. Similar treatment of the complex [Ru-(C6H4Me-4)Cl(CO)(PPh3)2] leads to the related sigma-tolyl derivative [Ru(C6H4Me-4)(CO)(PPh3)(9-S3)]Cl. The analogous reactions of 9-S3 with the related thiocarbonyl complexes [Ru(CR=CHPh)Cl(CS)(PPh3)2] (R = H, Ph) and [Ru{C(CO2Me)=CHCO2Me}Cl(CS)(PPh3)2] provide the cationic complexes [Ru(eta-2-SCCR=CHR)(PPh3)(9-S3)]+ and [Ru{C(C(CO2Me)=CHCO2Me}(CS)(PPh3)(9-S3)]+, the former via vinyl-thiocarbonyl ligand coupling.