Self-assembled chloro-bridged metallo-prismatic cations of the general formula [M6(η5-C5Me5)6(μ3-tpt)2(μ-Cl)6]6+ (M = Rh, Ir; tpt=2,4,6-tri(pyridin-4-yl)-1,3,5-triazine)

Two cationic pentamethylcyclopentadienyl metal-based hexanuclear complexes with trigonal prismatic architecture have been synthesised through a two-step strategy. The dinuclear complexes [M(eta(5)-C5Me5)(mu-Cl)Cl](2) (M = rhodium and iridium) react with 2,4,6-tri(pyridin-4-yl)-1,3,5-triazine (tpt) in dichloromethane to give the trinuclear complexes [Rh-3(eta(5)-C5Me5)(3)(mu(3)-tpt)Cl-6] (1) and Ir-3(eta(5)-C5Me5)(3)(mu(3)-tpt)Cl-6] (2), respectively. Addition of silver triflate to I and 2 in dichloromethane connects two identical triangular panels to form the hexanuclear metallo-prismatic cations [Rh-6(eta(5)-C5Me5)6([mu(3)-tpt)(2)(mu-Cl)(6)](6+) (3) and [Ir-6(eta(5)-C5Me5)(6)(mu(3)-tpt)(2)(mu-Cl)(6)](6+) (4), respectively. Cations 3 and 4 have been isolated as their triflate salts and characterised by H-1 NMR, IR and UV/visible spectroscopy. (c) 2007 Elsevier B.V. All rights reserved.