Reactivity towards nitriles, cyanamides, and carbodiimides of palladium complexes derived from benzyl alcohol. Synthesis of a mixed Pd2Ag complex.

The chelate complex [Pd(κ(2)-C,O-C6H4CH2O-2)(bpy)] () reacts with acetonitrile, cyanamides, or carbodiimides, in the presence of AgOTf (1 : 5 : 1 molar ratio) and residual water, to form complexes [Pd{κ(2)-C,N-C6H4{CH2OC([double bond, length as m-dash]NX)Y}-2}(bpy)](OTf), where X = H, Y = Me (), NMe2 (), NEt2 (), X = R, Y = NHR (R = (i)Pr (), Tol ()), as a result of the insertion of the unsaturated reagent into the O-Pd bond of and the protonation of one of the N atoms. In the absence of AgOTf the reaction of with TolN[double bond, length as m-dash]C[double bond, length as m-dash]NTol (Tol = p-Tolyl) results in the formation of the neutral complex [Pd{κ(2)-C,N-C6H4{CH2OC([double bond, length as m-dash]NTol)NTol}-2}(bpy)] (). Complexes and can be interconverted by deprotonation ( + KO(t)Bu) or protonation ( + KOTf + HOTf) reactions. When the reaction of with TolN[double bond, length as m-dash]C[double bond, length as m-dash]NTol in the presence of AgOTf is carried out in a 1 : 1 : 1 stoichiometric ratio, or for a short period of time, a mixture of and a mixed heterometallic Ag2Pd complex is obtained ( = [Ag(N-)2](OTf)). Complex is the major product when the AgOTf is added before the carbodiimide, and the reaction is stopped immediately. can also be obtained by reaction of with 0.5 equiv. of AgOTf. When complex [PdI(C6H4CH2OH-2)(bpy)] () reacts with (i)PrN[double bond, length as m-dash]C[double bond, length as m-dash]N(i)Pr in the presence of TlOTf, instead of AgOTf, a ca. 1 : 1 mixture of and [Pd{κ(2)-O,N-OCH2{C6H4{C([double bond, length as m-dash]NH(i)Pr)N(i)Pr}-2}}(bpy)](OTf) () forms. Complex is the result of the insertion of the carbodiimide into the C-Pd bond. Complexes have been extensively characterized by NMR spectroscopy, and the crystal structures of , , and ·2.5CHCl3·0.5Et2O have been determined by X-ray diffraction studies.