Synthesis, structure and reactivity of the thioether half-sandwich rhodium(III) complex [RhCl(MeCN)2([9]aneS3)][CF3SO3]2([9]aneS3= 1,4,7-trithiacyclononane)

Abstract

The complex [RhCl(MeCN)₂([9]aneS₃)][CF₃SO₃]₂1([9]aneS₃= 1,4,7-trithiacyclononane) was prepared by reaction of RhCl₃·3H₂O with [9]aneS₃ in the presence of an excess of Ag(O₃SCF₃) in acetonitrile. It has been employed as a starting material for the synthesis of the mixed-ligand sandwich complex [Rh{HB(pz)₃}([9]aneS₃)][CF₃SO₃]₂2(pz = pyrazol-l-yl) and the half-sandwich complexes [RhCl(pymt)([9]aneS₃)][CF₃SO₃]3(Hpymt = pyrimidine-2-thiolate), [Rh(pymt)₂([9]aneS₃)][CF₃SO₃]4 and [RhCl(S₂CNEt₂)([9]aneS₃)][CF₃SO₃]5. Treatment of 1 with 2 molar equivalents of Na[S₂CNEt₂] in methanol led to a base-induced ring opening of the thioether [9]aneS₃ and formation of the µ-S bridged dinuclear complex [{Rh(S₂CNEt₂)₂}₂{µ-S(CH₂)₂S(CH₂)₂SCHCH₂}₂]6. The structures of 1–3 and 6 have been determined by X-ray crystallography.