Reaction of the trithia ligands 9S3 (1,4,7-trithiacyclononane), IOS3 (1,4,7-!rithiacyclodecane), 12S3 (1,5,9-trithiacyclododecane), and ttn (2,5&trithianonane) with rhodium(lI1) triflate in methanol yields the homoleptic thioether complexes [Rh(L) 13+ (L = 9S3, 10S3, 12S3, and ttn). Average Rh-S distances in these cations increase from 2.34 A in the 9S3 complex to 2.36 . k in the 12S3 analogue. Cyclic voltammetry in MeNO, shows that [Rh(9S3)2j3+ undergoes two one-electron reductions.The first of these corresponds to a discrete mononuclear Rh(ll) complex that has been characterized by EPR as well as electrochemical methods. The 10S3 analogue, [Rh( 10S3)2]3+, behaves similarly. In the 12S3 analogue the quasi-reversible Rh(lll/ll) couple contrasts with the irreversibility of the Rh(II/l) process. In continuation of this trend, the acyclic complex [Rh(ttn)J'+ shows no reversible electrochemistry. The conformational properties of the macrocyclic ligand play a crucial role in stabilizing [Rh(L)2]2+ complexes, as shown by their increasing stability to disproportionation in the order L = 9S3 > IOS3 > 12S3 >> ttn. Crystal data: [Rh(9S3),](CF3SO3) , RhCI5H2&F9O9, fw = 910.83, monoclinic, space group C2/c (no. 15), a = 18.638 (6) A, b = 10.643 (3) A, c = 16.075 ( 2 ) A,@ = 105.93 (2)O, Z = 4; [Rh(12S3)2](BF4)3. RhCI8H3,S6B3Fl2, fw = 808.2, monoclinic, space group P2,/c (no. 14), a = 17.673 (5) A, b = 10.874 (4) A, c = 17.164 (3) A, @ = 110.85 (I)', z = 4. ( 2 5 ) Seizer. W. N.; Ogle, C. A.; Wilson, G . S.; Glass. R. S. Inorg. Chem. 1983. 22, 266.