Solvolysis, structure and reactivity of (1,4,7-trimethyl-1,4,7-triazacyclononane)rhodium(III) complexes [RhCl3-xLx(Me-3[9]aneN(3))]((x)+) (L = CH3CN,DMSO, DMF) and [RhCl(pyz)(2)(Me-3[9]aneN(3))] (Hpyz = pyrazole)

Treatment of [RhCl3(Me-3[9]aneN(3))] (1) (Me[9]aneN(3) = 1,4,7-trimethyl-1, 4,7-triazacyclononane) with Ag(CF3SO3) in a 1:3 ratio at 60 degrees C for 3 0 min in CH3CN leads to formation of the tetranuclear complex [{RhCl3(Me-3[ 9]aneN(3))}(2)Ag-2(CF3 SO3)(CH3CN)](CF3SO3). CH3CN (2) with a novel Rh2Ag2C l6 core. More forcing conditions (reflux, 18 h) afford the likewise tetranu clear complex [{RhCl2(CH3CN)(Me-3[9]aneN(3))}(3)Ag](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-kappa O)(Me-3[9]aneN(3))} Ag-2(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)(Me-3[9]aneN(3))](CF3SO3)(2) (5). The coordinated DMF ligands are transformed to CH3NHCHO in [RhCl(CH3NHCHO) (2)(Me-3[9]aneN(3))](CF3SO3)(2) (6) on treating 5 with methylamine. [RhCl(m u-pyz)(2)(Me-3[9]aneN(3))] (7) (pyz=pyrazolate) reacts with (eta(5)-C5Me5)M (III) fragments to generate the dinuclear complexes [{Rh(Me-3[9]aneN(3))} ( mu-Cl)(mu-pyz)(2){M(eta(5)-C5Me5)}](CF3SO3)(2) 8 and 9 (M = Rh, Ir). X-ray structures have been determined for 2-8. (C) 2000 Elsevier Science S.A. All rights reserved.