Insights into the Cascade Reaction of CO and Heteroallenes Mediated by Dinitrogen Hafnocene Complexes: The Indirect Effect of Nitride's Nucleophilicity. Issue 14 (18th February 2016)

• Record Type: Journal Article
• Authors: Kefalidis, Christos E.; Maron, Laurent
• Is Part Of: Chemistry. Volume 22:Issue 14(2016)
• Page Start: 4743
• Page End: 4747
• Publication Date: 2016-02-18
• Subjects: carbon dioxide -- density functional calculations -- hafnium -- nitrides -- reaction mechanisms; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201600059
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: A DFT mechanistic exploration of the reactivity of the dinitrogen hafnocene complex, [{(η 5 ‐C5 H2 ‐1, 2, 4‐Me3 )2 Hf}2 (μ2 ‐N2 )], towards mixtures of CO/CO2 and CO/OCN t Bu is reported. The crucial role of the nitride intermediate is highlighted, as well as the importance of the bridging mode of the cyanate ligand between the two Hf metal atoms throughout the process. Interestingly, the CO2 addition to the nitride intermediate occurs through an outer‐sphere transition state, whereas the addition of the heteroallene is governed by the steric congestion imposed by cyclopentadienyl ligands. Abstract : Nucleophilicity rules ! A DFT mechanistic exploration of the reactivity of a dinitrogen hafnocene complex towards mixtures of CO/CO2 and CO/OCN t Bu is reported. The crucial role of the nitride intermediate is highlighted, as well as the importance of the bridging mode of the cyanate ligand between the two Hf metal atoms.