ISSN:
1572-901X
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
Notes:
Summary Reaction of [RuCl2(PPh3)3] with one molar equivalent of [15]aneS2O3 yields the complex [RuCl2(PPh3)2 ([15]aneS2O3)]. Reaction of two equivalents of [15]-aneS2O3 or [18]aneS2O4 with [RuCl2(PPh3)3] yields the complex cations [RuCl(PPh3) ([15]aneS2O3)2]+ and [RuCl(PPh3)([18]aneS2O4)2]+, respectively. The complex [RuCl2(PPh3)2([15]aneS2O3)]·1/2Et2O shows RuII in an octahedral Cl2S2P2 environment: 600-01(1), 2.4447(15); 600-02(2), 2.4154(15); 600-03(1), 2.4085(15); 600-04(4), 2.4215(16); 600-05(1), 2.3775(6); and 600-06(2), 2.3640(15) Å. 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(PPh3)([18]aneS2O4)] PF6·1/2EtOH shows the RuII in an octahedral ClS4P environment: 600-07, 2.441(6); 600-08, 2.340(5); 600-09(1), 2.387(5); 600-10(4), 2.389(6); 600-11(1′), 2.348(6); and 600-12(4′), 2.438(6) Å. The Cl− and PPh3 ligands adopt a cis configuration in contrast to the reported analogous [15]aneS2O3 complex which shows a trans configuration. 31P-n.m.r. spectroscopic studies show the presence of two geometric isomers in both cases. Reactions of [18]aneS2O4 with [Ru2Cl4(C6H6)2] and [Ru(Cp)Cl(PPh3)2] yields the complexes [RuCl(C6H6)-([18]aneS2O4)]+ and [RuCp(PPh3)([18]aneS2O4)]+, respectively. The complex [RuCl(C6H6)([18]aneS2O4)]-PF6 shows the Cl− ligand and the two thioether S-donors of [18]aneS2O4 coordinated to the [Ru(C6H6)] fragment: 600-13, 2.416(2); 600-14(1), 2.382(5); and 600-15(4), 2.377(5) Å. The single crystal structure of [RuCl(C6H6)-([18]aneS2O4)]BPh4 shows a similar geometry around the RuII ion: 600-16, 2.411(6); 600-17(1), 2.384(6); and 600-18(4), 2.369(6) Å. [Ru(C5H5)(PPh3)([18]ane-S2O4)]PF6 shows the PPh3 ligand and [18]aneS2O4 coordinated to the pseudo-octahedral RuII fragment: 600-19, 2.3126(17); 600-20(1), 2.3793(17); and 600-21(4), 2.3587(19) Å.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF00136428
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