| dc.description |
Reaction of [Ir4(CO)12] or [Ir6(CO)16] in tetrahydrofuran with SCN<sup>â </sup>, SeCN<sup>â </sup> or polysulphides in MeOH gives the trinuclear anions [Ir3(µ3-X)2(CO)6]<sup>â </sup>(X = S or Se) which have been isolated and investigated by X-ray analysis. The salt [NMe3(CH2Ph)][Ir3(µ3-S)2(CO)6](1) crystallizes in the monoclinic space group P21/n(no. 14) with a= 9.303(2), b= 17.295(3), c= 28.274(4)à , β= 94.19(2)°, Z= 8, R= 0.027 for 3 676 significant independent reflections having I > 3Ï (I). The salt [NMe4][Ir3(µ3-Se)2(CO)6](2) crystallizes in the monoclinic space group C2/c(no. 15) with a= 15.930(3), b= 7.877(2), c= 15.040(2)à , β= 108.22(2)°, Z= 4, R= 0.025 for 1 045 significant independent reflections having I > 3Ï (I). Both structures were solved by conventional Patterson and Fourier methods and refined by full-matrix least-squares methods. The anions consist of an Ir3 triangle bicapped by triply bridging chalcogenide atoms. Each iridium atom, bearing two terminal CO groups, displays an almost square-planar geometry with respect to the ligands. In both compounds the Irâ Ir distances are long [mean values 3.086(1) and 3.170(1)à for compounds (1) and (2) respectively] and suggest a very weak (if any) metalâ metal interaction. The two anions can be considered therefore as trinuclear Ir<sup> I </sup> metal aggregates rather than triangular clusters. |
