Organometallic macrocycle chemistry .5. sigma-vinyl and sigma-aryl complexes of ruthenium(II) ligated by 1,4,7-trithiacyclononane: X-ray crystal structure of [Ru(CH=CH2)(CO)(PPh(3))([9]aneS(3))]PF6 center dot 2CH(2)Cl(2)

The reaction of coordinatively unsaturated sigma-vinyl complexes [Ru(CR=CHR')(CO)(PPh(3))- with 1,4,7-trithiacyclononane ([9]aneS(3)) provides chiral salts of the ''half-sandwich'' complexes [Ru(CR=CH2)(Co)(PPh(3))-([9]aneS(3))](+). The synthesis of the sigma-aryl complex [Ru(C(6)H(4)Me-4)(CO)(PPh(3))([9]aneS(3))](+) is also described. A representative NMR study of one example allowed the assignment of individual chemical shifts for the 12 diastereotopic proton environments of the macrocycle. The crystal structure of [Ru(CH=CH2)(CO)(PPh(3))-([9]aneS(3))]PF(6)2CH(2)Cl(2) is also reported.