Naphthyl-(2-pyridylmethylene)amine complexes of silver(I) and ruthenium(II): synthesis, spectral studies and electrochemical behaviour

Pyridine-2-carboxaldehyde reacts with α/β-naphthylamine to give α/β-naphthyl-(2-pyridylmethylene)amine [α-L (1), β-L (2)]. L belongs to the unsymmetric diimine (—N=C—C=N—) family which can form five–membered chelate rings with metal ions. {donor centers are abbreviated as N[N(Py)] and N′[N(nap)]} [Ag(L)2]+ complexes were prepared and characterized by spectroscopic data. The reaction between L and RuCl3 in boiling EtOH yielded green and blue–green compounds of composition RuCl2(L)2. I.r., u.v.–vis. and 1H-n.m.r. data determined the stereochemistry of the complexes as trans-cis-cis (green) and cis-trans-cis (blue–green) according to the sequence of the coordination pair of Cl, N [N(Py)] and N′ [N(nap)]. Upon treatment of Ag(L)2+ with Ru(bpy)2Cl2 in alcoholic suspension the ternary complexes, [Ru(bpy)2(L)](ClO4)2, were isolated and characterized by spectroscopic data. [Ru(bpy)(L)2](ClO4)2 complexes were synthesized similarly from ctc-Ru(L)2Cl2 and 2,2′-bipyridine (bpy) in the presence of AgNO3 and NaClO4. These complexes show well-defined m.l.c.t transitions in the visible region. The sterochemistry of the complexes was established by 1H-n.m.r. data. Cyclic voltammetry shows a high potential RuIII/RuII couple and follows the order: [Ru(bpy)(L)2]2+ > [Ru(bpy)2(L)]2+ > Ru(β-L)2Cl2 > Ru(α-L)2Cl2.