Reactions of the homoleptic acetonitrile complexes of palladium and platinum with diethylamine

The homoleptic M(MeCN)₄]²⁺ cations (M = Pd, Pt) as the tetrafluoroborato derivatives were reacted with NHEt₂. The platinum species affords the amidino derivative {Pt(E)-HNC(NEt₂)Me]₄}BF₄]₂, 1, as the only detected product of the addition of the amine to the coordinated nitrile. On the contrary, for Pd(MeCN)₄]BF₄]₂ competition between the substitution of the nitrile and addition of the amine to the nitrile group is operative: by carrying out the reaction in acetonitrile as solvent, complete conversion was obtained to the crystallographically defined {Pd(E)-HNC(NEt₂)Me]₄}BF₄]₂. Consistent with these findings, PdCl₂(MeCN)₂ reacts with NHEt₂ in acetonitrile yielding the substitution complex PdCl₂(NHEt₂)₂, whereas the amidino complex cis-PtCl₂(E)-HNC(NEt₂)Me]₂, 3 was obtained from PtCl₂(MeCN)₂. Complex 3 was characterized by X-ray diffractometry.