Bridge cleavage reactions of cyclopalladated nitrosamines with thioamides and related compounds

The palladacycle Pd(μ-O₂CMe){κ²C,N-4-MeC₆H₃N(Me)NO}]₂ readily undergoes bridge cleavage reactions with a variety of compounds containing donor functionalities including thioamides, 8-hydroxyquinoline, thioureas, selenoureas, acetylacetone derivatives, dithiocarbamates, xanthates, as well as bidentate N-donors to afford either the monomeric, neutral Pd(II) complexes Pd{κ²C,N-4-MeC₆H₃N(Me)NO}{L-L}] or the monocationic complexes Pd{κ²C,N-4-MeC₆H₃N(Me)NO}(N-N)]PF₆ in high yields. A series of 15 different complexes was prepared and fully characterised spectroscopically and, in some cases, by X-ray diffraction. It was also found that the dithiocarbamato complex undergoes a disproportionation reaction in solution to give the bis(cyclometallated) complex Pd{κ²C,N-4-MeC₆H₃N(Me)NO}₂] as well as the bis(dithiocarbamato) complex Pd{κ²S-S₂CNEt₂}₂].