Abstract
The cluster [HIr5(CO)12]2- (1) was prepared by condensation of [HIr4(CO)11]- and [Ir(CO)4]- (molar ratio 1:1) in refluxing THF, with almost quantitative yields. Its solid state structure was determined by X-ray diffraction at low temperature on the salt [PPh3CH2Ph]2[HIr5(CO)12]. The metal atoms define a trigonal bipyramidal arrangement. The hydride ligand was located indirectly as a bridge between apical and equatorial metal atoms. The phosphine-substituted cluster [HIr4(CO)10PPh3]- (2) was synthetized by CO displacement on [HIr4(CO)11]-, in THF at room temperature. This reaction is selective, with no traces of polysubstitution products. In the solid state, the hydride and the triphenylphosphine are axially bound on basal iridium atoms; the terminal hydrogen atom was directly located by X-ray analysis at a Ir–H distance of 1.57(9) Å. On the contrary, two isomers are present in THF solution, and they interconvert rapidly at room temperature, as shown by1H and 31P NMR spectra.
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Della Pergola, R., Garlaschelli, L., Manassero, M. et al. Iridium Cluster Chemistry: The Synthesis and the Solid State Structures of [HIr5(CO)12]2− and [HIr4(CO)10PPh3]−. Journal of Cluster Science 12, 23–34 (2001). https://doi.org/10.1023/A:1016658625915
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DOI: https://doi.org/10.1023/A:1016658625915