American Chemical Society
om401001p_si_002.cif (60.96 kB)

Structure and Bonding of a Zwitterionic Iridium Complex Supported by a Phosphine with the Parent Carba-closo-dodecaborate CB11H11 Ligand Substituent

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posted on 2013-12-09, 00:00 authored by Ahmad El-Hellani, Christos E. Kefalidis, Fook S. Tham, Laurent Maron, Vincent Lavallo
A zwitterionic iridium complex of a phosphine, bearing the carba-closo-dodecaborate anion as a ligand substituent, is reported. When tethered directly to a phosphine ligand, the CB11H11 R group engages in agostic-like bonding, utilizing the B–H bonds adjacent to the carbon atom in the cluster. Evidence for the interactions is observed in solution by variable-temperature NMR and also in the solid state by a single-crystal X-ray diffraction study. The bonding between the cluster and the iridium center has also been analyzed computationally and can be described as a double agostic bonding augmented by an overlap of the skeletal electrons of the cluster with the dz2 orbital of the metal. A significant lengthening of a trans-olefin C–C bond suggests that this ligand substituent has a pronounced trans influence, which is in contrast to the unfunctionalized weakly coordinating HCB11H11 anion.