Ruthenium complexes of thioether/oxa ionophores: The synthesis and single-crystal X-ray structures of [RuCl2(PPh(3))(2)([15]aneS(2)O(3))], [RuCl(PPh(3))([18]aneS(2)O(4))(2)]PF6, [RuCl(p-MeC(6)H(4)i-Pr)([15]aneS(2)O(3))]PF6, [RuCl(C6H6)([18]aneS(2)O(4))]X (X=PF6 or BPh(4)) and [Ru(C5H5)(PPh(3))([18]aneS(2)O(4))]PF6, ([15]aneS(2)O(3)=1,4,7-trioxa-10,13-dithiacyclopentadecane; [18]aneS(2)O(4)=1,4,7,10-tetraoxa-13,16-dithiacyclooctadecane)

Reaction of [RuCl2(PPh(3))(3)] with one molar equivalent of [15]aneS(2)O(3) yields the complex [RuCl2(PPh(3))(2) ([15]aneS(2)O(3))]. Reaction of two equivalents of [15]aneS(2)O(3) or [18]aneS(2)O(4) with [RuCl2(PPh(3))(3)] yields the complex cations [RuCl(PPh(3)) ([15]aneS(2)O(3))(2)](+) and [RuCl(PPh(3))([18]aneS(2)O(4))(2)](+), respectively. The complex [RuCl2(PPh(3))(2)([15]aneS(2)O(3))]. 1/2Et(2)O shows Ru-II in an octahedral Cl2S2P2 environment: Ru-Cl(1), 2.4447(15); Ru-Cl(2), 2.4154(15); Ru-S(1), 2.4085(15); Ru-S(4), 2.4215(16); Ru-P(1), 2.3775(6); and Ru-P(2), 2.3640(15) Angstrom. The phosphine ligands are mutually cis and in common with the thioether S-donors of the macrocycle occupy equatorial binding sites; the Cl- ligands are in apical positions. The complex [RuCl(PPh(3))([18]aneS(2)O(4))] PF6 . 1/2EtOH shows the Ru-II in an octahedral ClS4P environment: Ru-Cl, 2.441(6); Ru-P, 2.340(5); Ru-S(1), 2.387(5); Ru-S(4), 2.389(6); Ru-S(1'), 2.348(6); and Ru-S(4'), 2.438(6) Angstrom. The Cl- and PPh(3) ligands adopt a cis configuration in contrast to the reported analogous [15]aneS(2)O(3) complex which shows a trans configuration, P-31-n.m.r. spectroscopic studies show the presence of two geometric isomers in both cases. Reactions of [18]aneS(2)O(4) with [Ru2Cl4(C6H6)(2)] and [Ru(Cp)Cl(PPh(3))(2)] yields the complexes [RuCl(C6H6)([18]aneS(2)O(4))](+) and [RuCp(PPh(3))([18]aneS(2)O(4))](+), respectively. The complex [RuCl(C6H6)([18]aneS(2)O(4))]PF6 shows the Cl- ligand and the two thioether S-donors of [18]aneS(2)O(4) coordinated to the [Ru(C6H6)] fragment: Ru-CI, 2.416(2); Ru-S(1), 2.382(5); and Ru-S(4), 2.377(5) Angstrom. The single crystal structure of [RuCl(C6H6)([18]aneS(2)O(4))]BPh(4) shows a similar geometry around the Ru-II ion: Ru-Cl, 2.411(6); Ru-S(1), 2.384(6); and Ru-S(4), 2.369(6) Angstrom. [Ru(C5H5)(PPh(3))[18]aneS(2)O(4))]PF6 shows the PPh(3) ligand and [18]aneS(2)O(4) coordinated to the pseudo-octahedral Ru-II fragment: Ru-P, 2.3126(17); Ru-S(1), 2.3793(17); and Ru-S(4), 2.3587(19) Angstrom.