| Abstract
| - Optically active compounds Ru(P(OE)3)3S5 (E = Me and Et) were synthesized and crystallized in the space groups P31 (E = Me) and P212121 (E = Et). The crystal structures show that the pentasulfide S52- acts as the first tridentate chelating ligand. The ligand S52- was fragmented to S2- and S22- when the compounds were reacted with PR3 (R = Ph, OMe and Et) and RuCl2(P(OE)3)4 (E = Me and Et).
- Room temperature stirring of H2Ru(P(OE)3)4 (E = Me and Et) and elemental sulfur in benzene afforded theoptically active compounds Ru(P(OMe)3)3S5 (1) and Ru(P(OEt)3)3S5 (2). Compounds 1 and 2 are crystallized inthe trigonal space group P31 with a = 14.231(10) Å, c = 10.24(1) Å, V = 1794(2) Å3, and Z = 3, and orthorhombicspace group P212121 with a = 15.393(5) Å, b = 18.126(6) Å, c = 12.421(4) Å, V = 3465(1) Å3, and Z = 4,respectively. Solutions of 1 and 2 did not show any optical activity since the bulk materials are racemic mixtures.The X-ray analyses also reveal that in both compounds polysulfide S52- ion acts as a novel tridentate ligand,resulting in an asymmetric bicyclic RuS5 unit having three- and five-membered rings around the ruthenium atom.Fragmentation of the S52- ring to S2- ion was observed in the presence of sulfur-abstracting reagents such as PR3(R = Ph, OMe, and OEt) and also to S22- ion when the compounds were reacted with RuCl2(P(OE)3)4 (E = Meand Et).
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