The reaction of iridium(iii) hydride complex 1 based on the pincer dibenzobarrelene ligand (HOCH2)2(PCsp3P) with pyridine proceeds stepwise to show different reactivities of the starting fac-isomers 1A and 1B. The kinetic product of the reaction is mer-complex 2 with a trans disposition of the pyridine and hydride ligands. Isomerization into the thermodynamic product 2′ containing pyridine in the cis-position with regard to hydride proceeds slowly. The estimation of activation parameters (ΔH≠ and ΔS≠) shows that the change in the geometry of fac-complexes upon coordination of pyridine occurs through an associative transition state, while isomerization of the mer-complexes is a dissociative process. The isomers of complex 1 and its pyridine-containing derivatives 2 and 2′ are shown to exhibit different reactivities in the formation of dihydrogen bond and the catalytic dehydrogenation of PriOH under model conditions.
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- IR spectroscopy
- NMR spectroscopy
- hydrogen bonds
- transition metal hydrides