Assessing the Metal–Metal Interactions in a Series of Heterobimetallic Nb/M Complexes (M = Fe, Co, Ni, Cu) and Their Effect on Multielectron Redox Properties

A one-pot synthetic procedure for a series of bimetallic Nb/M complexes, Cl–Nb(iPrNPPh2)3M–X (M = Fe (2), Ni (4), Cu (5)), is described. A similar procedure aimed at synthesizing a Nb/Co analogue instead affords iPrN═Nb(iPrNPPh2)2(μ-PPh2)Co–I (3) through cleavage of one phosphinoamide P–N bond under reducing conditions. Complexes 4and 5are found to have short Nb-M distances, corresponding to unusual metal–metal bonds between Nb and these first row transition metals. For comparison, a series of heterobimetallic O≡Nb(iPrNPPh2)3M–X complexes (M = Fe (7), Co (8), Ni (9), Cu (10)) was synthesized. In these complexes, the NbVcenter is engaged in sufficient π-bonding to the terminal oxo ligand to remove the driving force for direct metal–metal interactions. A comparison of the cyclic voltammograms of 2and 4–10reveals that the presence of a second metal shifts the redox potentials of both Nb and the late metal center anodically, even when direct metal–metal interactions are not present.