Solvolysis, structure and reactivity of (1,4,7-trimethyl-1,4,7-triazacyclononane)rhodium(III) complexes [RhCl3−xLx(Me3[9]aneN3)](x)+ (L=CH3CN, DMSO, DMF) and [RhCl(pyz)2(Me3[9]aneN3)] (Hpyz=pyrazole)

Treatment of [RhCl3(Me3[9]aneN3)] (1) (Me[9]aneN3=1,4,7-trimethyl-1,4,7-triazacyclononane) with Ag(CF3SO3) in a 1:3 ratio at 60°C for 30 min in CH3CN leads to formation of the tetranuclear complex [{RhCl3(Me3[9]aneN3)}2Ag2(CF3 SO3)(CH3CN)](CF3SO3)·CH3CN (2) with a novel Rh2Ag2Cl6 core. More forcing conditions (reflux, 18 h) afford the likewise tetranuclear complex [{RhCl2(CH3CN)(Me3[9]aneN3)}3Ag](CF3 SO3)4 (3) with an alternative Rh3AgCl6 central unit. Whereas only one Cl− ligand can also be substituted under similar conditions in DMSO to provide trinuclear [{RhCl2(DMSO-κO)(Me3[9]aneN3)}2Ag(CH3OH)](CF3SO3)3 (4), performing the reaction in the more polar solvent DMF allows two chlorides to be removed thereby yielding mononuclear [RhCl(DMF)2(Me3[9]aneN3)](CF3SO3)2 (5). The coordinated DMF ligands are transformed to CH3NHCHO in [RhCl(CH3NHCHO)2(Me3[9]aneN3)](CF3SO3)2 (6) on treating 5 with methylamine. [RhCl(μ-pyz)2(Me3[9]aneN3)] (7) (pyz=pyrazolate) reacts with (η5-C5Me5)M(III) fragments to generate the dinuclear complexes [{Rh(Me3[9]aneN3)}(μ-Cl)(μ-pyz)2{M(η5-C5Me5)}](CF3SO3)28 and 9 (M=Rh, Ir). X-ray structures have been determined for 2–8.