Modulation of Isomerization and Ligand Exchange Rates by π Bonding in Bis(iminoxolene)iridium Pyridine Complexes.

The bis(iminoxolene)iridium complex (Diso) ₂ IrCl (Diso = N -(2,6-diisopropylphenyl)-4,6-di- tert -butyl-2-imino- o -benzoquinone) reacts with pyridine to give trans -(Diso) ₂ Ir(py)Cl as the kinetic product, with cis -(Diso) ₂ Ir(py)Cl formed as the exclusive thermodynamic product upon heating. Electronic spectra and density functional theory calculations point to very similar electronic structures for the cis and trans isomers, with a nonbonding iminoxolene-centered HOMO and a metal-iminoxolene π* LUMO. The triplet states of cis -(Diso) ₂ Ir(py)Cl and cis -[(Diso) ₂ Ir(py) ₂ ] ⁺ (but not trans -(Diso) ₂ Ir(py)Cl) are unusually low in energy (1000-1500 cm ^-1 above the singlets), as shown by variable-temperature NMR spectroscopy. The low-energy triplets are attributed to a change in dihedral angle in the iminoxolenes, which allows a partial π interaction that cannot be achieved in the trans octahedral compounds. Mechanistic studies of the trans-cis isomerization in toluene indicate that the reaction proceeds via isomerization of the five-coordinate species to a form with cis iminoxolene ligands and an apical oxygen. This form is high in energy due to the loss of a secondary iminoxolene-to-iridium π-donor interaction that is possible in the trans form but not in the cis form for the square pyramidal structures. This stereoelectronic effect, combined with the poorer binding of pyridine in trans -(Diso) ₂ Ir(py)Cl due to the interactions of the N -aryl substituents with the pyridine, makes the pyridine dissociate faster from the trans isomer by a factor of 10 ⁸ at room temperature.