Abstract
The stability constants and forward and reverse rate constants have been determined for adduct formation reactions involving tetra-μ-acetato, tetra-μ-propionate and tetrakis-μ-methoxyacetatodirhodium(II) with the ligands pyridine, picolinic acid, niacin and isonicotinic acid. The experimentally observed stability trend is isonicotinic acid > pyridine ⋍ niacin ⪢ picolinic acid. It appears that the π bonding ability of the ligands determines the order of stability of these adducts. The variation of the stabilities of the adducts formed from different tetra-μ-carbox-ybtodlrhodium(II) complexes and a given ligand is related to an inductive effect as well as the lipophylic nature of the carboxylate side chain. The more hydropholic character of the propionate species apparently exerts a desolvating effect at the two axial positions resulting in a more rapid ligand exchange.
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