Solvolysis Products of the Types [RhMeL2(Me3[9]aneN3)]2+ and [RuCl3—XLX(Me3[9]aneN3)](x)+ (x = 1‐2) and Preparation and Structure of [Ru([9]aneS3)(Me3[9]aneN3)](CF3SO3)2

Solvolysis of RhMe(CF₃SO₃)₂(Me₃9]aneN₃)] ( 1 ) (Me₃9]aneN₃ = 1, 4, 7‐trimethyl‐1, 4, 7‐triazacyclononane) in CH₃CN, DMSO or pyrazole (L) leads to substitution of both trifluoromethylsulfonate ligands and formation of the cationic complexes RhMeL₂(Me₃9]aneN₃)](CF₃SO₃)₂ 3—5 . In contrast, treatment of RuCl₃(Me₃9]aneN₃)] ( 2 ) with Ag(CF₃SO₃) in a 1:3 ratio for 2h in CH₃CN leads to formation of the tetranuclear complex {RuCl₃(Me₃9]aneN₃)}₂Ag₂(CF₃SO₃)(CH₃CN)](CF₃SO₃) · CH₃CN ( 6 ) with a novel (RuCl₃)₂Ag₂] core. More forcing conditions enable the substitution of respectively one or two chloride ligands by CH₃CN (reflux 18h) or DMF (85°C, 1h) to afford RuCl₂(CH₃CN)(Me₃9]aneN₃)](CF₃SO₃) ( 7 ) and RuCl(DMF)₂(Me₃9]aneN₃)](CF₃SO₃)₂ ( 8 ). The heteroleptic sandwich complex Ru(9]aneS₃)(Me₃9]aneN₃)](CF₃SO₃)₂ ( 9 ) can be prepared by reduction of 2 with Zn powder in acetone in the presence of 3 equiv. of Ag(CF₃SO₃), followed by addition of 9]aneS₃ (1, 4, 7‐trithiacyclononane). The redox potential E°(Ru³⁺/Ru²⁺) of +1.87 V vs NHE for 9 is only —0.12 V lower than that of the homoleptic complex Ru(9]aneS₃)₂]²⁺. Crystal structures are reported for 3 — 9 .