CATIONIC CYANOBENZYLPALLADIUM(II) COMPLEXES - SYNTHESIS AND REACTIVITY OF THE CN GROUP TOWARDS NUCLEOPHILES

The addition of alcohols, thiols, water and amines to the σ-coordinated CN group of cis-[Pd(o-CH2C6H4CN)L2]2(BF4)2(L2 = 2PPh3, 1,2-bis(diphenylphosphino)ethene or -ethane) yields stable N-bonded iminoether, iminothioether, amide and amidine complexes,respectively. Thiophenols, ArSH (Ar = p-C6H4CH3, p-C6H4Br) break the σ-PdC bond, forming o-cyano toluene and complexes of the type [Pd(SAr)L2]2(BF4)2. The azido complex PdN3(o-CH2C6H4CN)(Ph2PCH2CH2PPh2) is stable in the solid state but in solution it undergoes an intramolecular 1,3-cycloaddition yielding the corresponding tetrazolate complex. © 1979.