Selective cleavage of the two types of Pd–N bonds in di-µ-halogeno-bis[arylazo-oximatopalladium(II)]

Abstract

Triarylphosphines split the halogen bridge of the title complex and also open the arylazo-oximato chelate ring at the azo-end. In solution an equilibrium exists between the closed-ring and open-ring species. The equilibrium constants are reported. Bidentate phosphine and phosphinoarsine simultaneously split the bridge and cleave the Pd–N(azo) bond. Anhydrous HCI gas protonates the oximato-group with its concomitant displacement by Cl^– ion; in effect the Pd–N(oxime) bond is selectively cleaved.