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N-Insertion Reaction Mechanisms of Phenyl Azide with Hafnium Hydride Complex: A Quantum Chemistry Calculations

Abstract

Density functional theory (DFT) calculations have been performed to investigate the detailed mechanisms for the N-insertion reaction of phenyl azide with hafnium hydride complex. This reaction involves the intermolecular hydride transfer from the hafnium center of complex 1 Cp2*HfH2 to the terminal nitrogen atom of phenyl azide. Subsequently, the 1,3 hydrogen shift from the N1 atom to N3 atom takes place, accompanied by the cleavage of the N2−N3 bond to give amido complex 3 Cp2*HfH(NHPh) and dinitrogen. The further reaction is related to the intermolecular hydride transfer from the hafnium center to the N1′ atom of the second phenyl azide, followed by the formation of the final product bis(amido) complex 9 Cp2*HfH(NHPh)2 via the liberation of the second dinitrogen, which is the rate-determining step with an overall barrier of 29.8 kcal/mol. Frontier molecular orbital theory analysis shows that phenyl azide is activated by nucleophilic attack by the hydride ligand, which is consistent with our previous studies of N2O activation by other transition-metal hydride complexes.

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Publication details

The article was received on 04 Feb 2017, accepted on 05 May 2017 and first published on 08 May 2017


Article type: Paper
DOI: 10.1039/C7NJ00411G
Citation: New J. Chem., 2017, Accepted Manuscript
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    N-Insertion Reaction Mechanisms of Phenyl Azide with Hafnium Hydride Complex: A Quantum Chemistry Calculations

    H. Xie, L. Wang, Y. Li, J. kuang, Z. Wu, T. Fan, Q. Lei and W. Fang, New J. Chem., 2017, Accepted Manuscript , DOI: 10.1039/C7NJ00411G

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