Abstract
NMR kinetic investigations have been carried out on systems containing the 1,5-cyclooctadiene complexes (COD)IrCl(L) as such or in combination with [(COD)IrCl] 2 or L(L=AsPh 3 or PPh 3). The results for mixtures of (COD)IrCl(L) and L indicate that at low temperatures (−70 to −40°) an exchange of L occurs via the five-coordinate species ( COD)IrCl(L) 2, which is in equilibrium with much smaller amounts of the ionic species [(COD)Ir(L) 2] +Cl −. With (COD)IrCl(AsPh 3) and [(COD)IrCl] 2 reactions of dissociated triphenylarsine with both the monomeric and dimeric complexes are observed. Linebroadening was not noted when triphenylarsine was replaced by triphenylphosphine. Furthermore, it was found that (COD)IrCl(AsPh 3) reacts with Cl − and 1,5-cyclooctadiene. The reaction with 1,5-cyclooctadiene does not involve exchange between the coordinated and the free diolefin. The results are compared with those of the isoelectronic and isostructural rhodium systems.
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