Synthesis, structure and reactivity of the thioether half-sandwich rhodium(III) complex [RhCl(MeCN)(2)([9]aneS(3))][CF3SO3](2)([9]aneS(3)=1,4,7-trithiacyclononane)

The complex [RhCl(MeCN)(2)([9]aneS(3))][CF3SO3](2) 1 ([9]aneS(3) = 1,4,7-trithiacyclononane) was prepared by reaction of RhCl3 . 3H(2)O with [9]aneS(3) 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]aneS(3))][CF3SO3](2) 2 (pz = pyrazol-1-yl) and the half-sandwich complexes [RhCl(pymt)([9]aneS(3))][CF3SO3] 3 (Hpymt = pyrimidine-2-thiolate), [Rh(pymt)(2)([9]aneS(3))][CF3SO3] 4 and [RhCl(S(2)CNEt(2))([9]aneS(3))][CF3SO3] 5. Treatment of 1 with 2 molar equivalents of Na[S(2)CNEt(2)] in methanol led to a base-induced ring opening of the thioether [9]aneS(3) and formation of the mu-S bridged dinuclear complex [{Rh(S(2)CNEt(2))(2)}(2){mu-S(CH2)(2)S(CH2)(2)SCH=CH2}(2)] 6 The structures of 1-3 and 6 have been determined by X-ray crystallography.