Premium
Insights into the Cascade Reaction of CO and Heteroallenes Mediated by Dinitrogen Hafnocene Complexes: The Indirect Effect of Nitride's Nucleophilicity
Author(s) -
Kefalidis Christos E.,
Maron Laurent
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201600059
Subject(s) - chemistry , steric effects , ketosteroid , nucleophile , reactivity (psychology) , cyanate , cyclopentadienyl complex , nitride , ligand (biochemistry) , metallocene , photochemistry , stereochemistry , computational chemistry , medicinal chemistry , catalysis , polymer chemistry , organic chemistry , receptor , medicine , biochemistry , polymer , alternative medicine , pathology , layer (electronics) , polymerization , isomerase , enzyme
A DFT mechanistic exploration of the reactivity of the dinitrogen hafnocene complex, [{(η 5 ‐C 5 H 2 ‐1,2,4‐Me 3 ) 2 Hf} 2 (μ 2 ‐N 2 )], towards mixtures of CO/CO 2 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 CO 2 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.