Zinc(II), Copper(II), and Nickel(II) Complexes of Bis(tripodal) Diamide Ligands - Reversible Switching of the Amide Coordination Mode upon Deprotonation

A series of dinuclear Zn(II), Cu(II) and Ni(II) complexes of two new bis‐tripodal ligands with aromatic (H2‐4a) and aliphatic (H2‐4b) diamide spacers has been synthesized and structurally characterized. Each of the two tripodal entities of the neutral dinucleating ligands coordinates to one metal ion via three amine functions and a carbonyl oxygen atom of the amide groups. Either trifluoroacetate counterions or solvent molecules complete the trigonal‐bipyramidal (Zn, 5a), square‐pyramidal (Cu, 6a and 6b), and octahedral (Ni, 7a and 7b) coordination environment at the metal centers. Complexes 5a, 6a, and 7a with the phenylene‐bridged diamide ligand are readily deprotonated by potassium tert‐butoxide effecting a rearrangement of the dinuclear complexes. In the resulting zinc and copper complexes 8 and 9, one of the metal centers is coordinated by three amine functions of a tripodal subunit and the two amidate nitrogen atoms of the deprotonated ligand 4a2– while the coordination geometry of the second metal atom remains unchanged. The analogous nickel compound crystallizes as neutral tetranuclear complex (10)2 with intermolecular coordination of two amide carbonyl oxygen atoms to the nickel atoms of an adjacent dinuclear complex. The resulting coordination mode with binding of all four donor functions of the diamide spacer to three discrete metal centers is to date unprecedented for ortho‐phenylene‐bridged acetamides. The rearrangement upon deprotonation has been shown to be fully reversible and the starting complexes can be retrieved upon protonation of the two amidate functions. Synthesis of the trinuclear zinc complex 11 with coordination of the two amidate nitrogen atoms to a third metal center was achieved via deprotonation of (H6‐4a)(CF3CO2)4 by three equivalents of diethylzinc. In protic solvents 11 rapidly rearranges to give the entropically favored dinuclear complex 8 with elimination of one equivalent of zinc trifluoroacetate. Dinuclear complexes of type 1 (M = ZnII, CuII, NiII) rearrange upon deprotonation of the amide N atoms of the dinucleating ligand to give complexes 2. In the rearrangement the coordination chemistry of one metal atom remains unchanged whilethe second one becomes coordinated by the two amidate nitrogen atoms generated by deprotonation and the aliphatic amine donors. The deprotonation/rearrangement reaction is reversibel.