The reaction between norbornene (C7H10) and Ir-6(CO)(16) in refluxing toluene yields the substituted cluster [Ir-6(CO)(14)(C7H8)]. In the solid state, the six iridium atoms define an octahedral metal cage, and one face is capped by the C7H8 ligand, coordinated through a 1,2-vinylidene unit. The loss of two hydrogen atoms from the olefin is, presumably, the result of a double oxidative addition of its C-H bonds, followed by elimination of a hydrogen molecule from the cluster. The bonding parameters of the organic fragment, as well as the architecture of the carbonyl ligands, closely match those found in the alkyne-substituted [Ir-6(CO)(14)(PhCCPh)] complex. The cluster [Ir-6(CO)(14)(C7H8)] was characterized through H-1-, C-13- and bidimensional COSY NMR.
DELLA PERGOLA, R., Garlaschelli, L., Manassero, M., Sansoni, M., Sironi, A., Strumolo, D. (2005). C-H and C-C bonds activation by iridium clusters: Synthesis and solid state structure of [Ir6(CO)14(μ3- η1:η2:η1-C7H 8)]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 690(21-22), 4768-4772 [10.1016/j.jorganchem.2005.07.071].
C-H and C-C bonds activation by iridium clusters: Synthesis and solid state structure of [Ir6(CO)14(μ3- η1:η2:η1-C7H 8)]
DELLA PERGOLA, ROBERTO;SIRONI, ANNALISA;
2005
Abstract
The reaction between norbornene (C7H10) and Ir-6(CO)(16) in refluxing toluene yields the substituted cluster [Ir-6(CO)(14)(C7H8)]. In the solid state, the six iridium atoms define an octahedral metal cage, and one face is capped by the C7H8 ligand, coordinated through a 1,2-vinylidene unit. The loss of two hydrogen atoms from the olefin is, presumably, the result of a double oxidative addition of its C-H bonds, followed by elimination of a hydrogen molecule from the cluster. The bonding parameters of the organic fragment, as well as the architecture of the carbonyl ligands, closely match those found in the alkyne-substituted [Ir-6(CO)(14)(PhCCPh)] complex. The cluster [Ir-6(CO)(14)(C7H8)] was characterized through H-1-, C-13- and bidimensional COSY NMR.
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