title: Insights into the Cascade Reaction of CO and Heteroallenes Mediated by Dinitrogen Hafnocene Complexes: The Indirect Effect of Nitride's Nucleophilicity.
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/OCNtBu 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.
authors: LPCNO (Laboratoire de Physique et Chimie des Nano-objets), INSA (Institut National des Sciences Appliquées), CNRS (Centre National de la Recherche Scientifique), UPS (Université Paul Sabatier), Université de Toulouse, 135 Avenue de Rangueil, 31077, Toulouse, France. christos.kefalidis@gmail.com.
authors: Christos E
authors: CE
authors: Kefalidis
authors: LPCNO (Laboratoire de Physique et Chimie des Nano-objets), INSA (Institut National des Sciences Appliquées), CNRS (Centre National de la Recherche Scientifique), UPS (Université Paul Sabatier), Université de Toulouse, 135 Avenue de Rangueil, 31077, Toulouse, France. laurent.maron@irsamc.ups-tlse.fr.
authors: Laurent
authors: L
authors: Maron
keywords: carbon dioxide; density functional calculations; hafnium; nitrides; reaction mechanisms