Dinuclear thioether half-sandwich ruthenium(II) complexes of the types [{RuL′([9]aneS3)}2(µ-L)n]2+(n= 1, L′= PPh3; n= 2, L′= MeCN), [{Ru([9]aneS3)}2(µ-L)2]2+ and [{Ru([9]aneS3)}2(µ-L)3]+ with heterocyclic thioamides L ([9]aneS3= 1,4,7-trithiacyclononane)

Abstract

Reaction of [Ru(MeCN)₃([9]aneS₃-κ³S)][CF₃SO₃]₂([9]aneS₃= 1,4,7-trithiacyclononane) with 1,3-benzothiazol-2-thione (Hbtt) and pyridine-2-thione (Hpyt) in methanol in a 1 : 1 molar ratio afforded dinuclear complexes [{Ru([9]aneS₃-κ³S)}₂(µ-L)₂][CF₃SO₃]₂(L = btt or pyt) in which the ligands exhibit a tridentate µ-1κS:2κ²N,S bridging mode. Crystallization of the btt complex from acetonitrile yielded [{Ru(MeCN)([9]aneS₃-κ³S)}₂(µ-btt)₂][CF₃SO₃]₂ with µ-S bridging ligands. A triply µ-S bridged complex [{Ru([9]aneS₃-κ³S)}₂(µ-btt)₃][CF₃SO₃] was obtained from [Ru(MeCN)₃([9]aneS₃-κ³S)][CF₃SO₃]₂ and btt^– in a 2 : 3 molar ratio. Fragments (Ph₃P)([9]aneS₃-κ³S)Ru^II can be bridged with tetra- or tri-dentate dtuc^2–(H₂dtuc = 2,4-dithiouracil) anions in [{Ru(PPh₃)([9]aneS₃-κ³S)}₂(µ-dtuc)]²⁺ and [{RuCl(PPh₃)([9]aneS₃-κ³S)}(µ-dtuc){Ru(PPh₃)([9]aneS₃-κ³S)}]⁺. The structures of four complexes have been determined by X-ray crystallography.