Side‐on Coordination in Isostructural Nitrous Oxide and Carbon Dioxide Complexes of Nickel. Issue 13 (17th February 2021)

• Record Type: Journal Article
• Authors: Puerta Lombardi, Braulio M.; Gendy, Chris; Gelfand, Benjamin S.; Bernard, Guy M.; Wasylishen, Roderick E.; Tuononen, Heikki M.; Roesler, Roland
• Is Part Of: Angewandte Chemie international edition. Volume 60:Issue 13(2021)
• Page Start: 7077
• Page End: 7081
• Publication Date: 2021-02-17
• Subjects: back bonding -- carbon dioxide -- N-heterocyclic carbenes -- nickel -- nitrous oxide; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202011301
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: A nickel complex incorporating an N2 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 CO2 complex reported for comparison features a very similar solid‐state structure. Computational studies revealed that η 2 ‐N2 O binds to nickel slightly stronger than η 2 ‐CO2 in this case, and comparably to or slightly stronger than η 2 ‐CO2 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 N2 O complex. Abstract : The characterization of η 2 ‐ N, N ′‐N2 O and CO2 complexes of nickel and the associated computational study reveal that the bonding ability of N2 O to nickel is intermediate between that of CO2 and that of H2 C=CH2 . It is shown that in general, N2 O η 2 ‐binds to metals comparably to or stronger than CO2, indicating that the rarity of η 2 ‐N2 O metal complexes is due mostly to its oxidizing character and not to its weak σ‐donating and π‐accepting properties.