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Double oxidative addition reaction of dihalomethane to dinuclear iridium(I) complexes: Preparation and properties of some methylene-bridged diiridium(III) complexes. X-ray structure of [IrI(μ-t-BuS)(CO)P(OMe)3]2[μ-CH2]
El Amane, Mohamed,Maisonnat, André,Dahan, Fran?oise,Pince, Robert,Poilblanc, René
, p. 773 - 780 (2008/10/08)
Thiolato-bridged diiridium(I) complexes [Ir(μ-t-BuS) (CO)L]2, 1, react with dihalomethane to yield quantitatively [IrX(μ-t-BuS)(CO)L]2[μ-CH2], 2 (X = I, L = CO, P(OMe)3, PPh3, PPh2Me, PMe3; X = Br, L = PPh3). Cis and trans isomers were observed in two cases. A crystal structure determination of [IrI(μ-t-BuS)(CO)(P(OMe)3]2(μ15-CH 2] was carried out by X-ray diffraction. The compound crystallizes in orthorhombic space group D2h15 - Pbca in a cell of dimensions a = 17.033 (3) A?, b = 15.632 (2), and c = 23.808 (3) A?, with Z = 8. On the basis of 3106 unique reflections having Fo2 > 4σ(Fo2), the structure was refined by full-matrix least-squares technique to conventional agreement indices of R = 0.024 and Rw = 0.027. Each iridium atom is octahedrally coordinated, being bound to one carbonyl, one phosphite, one iodide ligand, two bridging S atoms of the thiolato ligands, and the bridging C atom of the CH2 group. The phosphite ligands (and the carbonyl ligands) are in a trans arrangement. The t-Bu groups are in an anti conformation with respect to the Ir2S2 core. The IrIr separation is 3.1980 (4) A?. In solution, complexes 2 undergo syn-anti isomerization on the NMR time scale. The halogen abstraction reaction of 2 by silver(I) salts and the subsequent addition of nucleophilic reagents to the cationic species so obtained are described together with the molecular structure of the products.
