Cationic cyanobenzylpalladium(II) complexes. Synthesis and reactivity of the CN group towards nucleophiles

Abstract

The addition of alcohols, thiols, water and amines to the σ-coordinated CN group of cis-[Pd( o-CH 2C 6H 4CN)L 2] 2(BF 4) 2(L 2 = 2PPh 3, 1,2-bis(diphenylphosphino)ethene or -ethane) yields stable N-bonded iminoether, iminothioether, amide and amidine complexes,respectively. Thiophenols, ArSH (Ar = p-C 6H 4CH 3, p-C 6H 4Br) break the σ-PdC bond, forming o-cyano toluene and complexes of the type [Pd(SAr)L 2] 2(BF 4) 2. The azido complex PdN 3( o-CH 2C 6H 4CN)(Ph 2PCH 2CH 2PPh 2) is stable in the solid state but in solution it undergoes an intramolecular 1,3-cycloaddition yielding the corresponding tetrazolate complex.