Side‐on Coordination in Isostructural Nitrous Oxide and Carbon Dioxide Complexes of Nickel

A nickel complex incorporating an N(2)O ligand with a rare η(2)‐N,N′‐coordination mode was isolated and characterized by X‐ray crystallography, as well as by IR and solid‐state NMR spectroscopy augmented by (15)N‐labeling experiments. The isoelectronic nickel CO(2) complex reported for comparison features a very similar solid‐state structure. Computational studies revealed that η(2)‐N(2)O binds to nickel slightly stronger than η(2)‐CO(2) in this case, and comparably to or slightly stronger than η(2)‐CO(2) to transition metals in general. Comparable transition‐state energies for the formation of isomeric η(2)‐N,N′‐ and η(2)‐N,O‐complexes, and a negligible activation barrier for the decomposition of the latter likely account for the limited stability of the N(2)O complex.