Abstract

Palladium complexes of the type <i>cis</i>-PdL₂X₂ have been found to be unstable at room temperature and isomerize to the corresponding <i>trans</i> isomers. Neglecting lattice interactions, symmetry considerations would predict two Pd–N stretching vibrations. These vibrations have been observed at 495 and 476 cm⁻¹ for the <i>cis</i>-chloride isomer and at 480 and 460 cm⁻¹ for the <i>cis</i>-bromide isomer. The <i>trans</i> isomer, by the same considerations, should have but one Pd–N stretching vibration. This vibration was observed for the <i>trans</i>-chloride isomer at 496 cm⁻¹ and for the <i>trans</i>-bromide isomer at 490 cm⁻¹. It has been found that as isomerization proceeds, from the <i>cis</i> to the <i>trans</i> forms, the lower Pd-N stretching vibration decreases in intensity and eventually disappears. The intensity changes for these vibrations over a period of 72 h indicated that the reaction follows a first-order rate law. A reaction mechanism has been proposed.

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