Activation of Dinitrogen-Derived Hafnium Nitrides for Nucleophilic NC Bond Formation with a Terminal Isocyanate†
Scott P. Semproni
Department of Chemistry, Princeton University, Princeton, New Jersey, 08544 (USA)
Search for more papers by this authorCorresponding Author
Prof. Paul J. Chirik
Department of Chemistry, Princeton University, Princeton, New Jersey, 08544 (USA)
Department of Chemistry, Princeton University, Princeton, New Jersey, 08544 (USA)===Search for more papers by this authorScott P. Semproni
Department of Chemistry, Princeton University, Princeton, New Jersey, 08544 (USA)
Search for more papers by this authorCorresponding Author
Prof. Paul J. Chirik
Department of Chemistry, Princeton University, Princeton, New Jersey, 08544 (USA)
Department of Chemistry, Princeton University, Princeton, New Jersey, 08544 (USA)===Search for more papers by this authorWe thank the Director of the Office of Basic Energy Science Chemical Sciences Division, U.S. Department of Energy (DE-FG-02-05ER15659) for financial support. S.P.S. thanks the Natural Sciences and Engineering Research Council of Canada for a predoctoral fellowship.
Graphical Abstract
Better by Hf: Anion coordination to a bridging hafnocene nitride complex, prepared from CO-induced N2 cleavage, increases the nucleophilicity of the nitrogen atom, thus promoting additional NC bond formation with a typically inert terminal isocyanate ligand. This cascade sequence allows synthesis of otherwise challenging mono-substituted ureas using N2, CO, and an appropriate electrophile.
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