DFT Calculations on the Mechanism of Transition-Metal-Catalyzed Reaction of Diazo Compounds with Phenols: O-H Insertion versus C-H Insertion

Yuan Liu, Zhoujie Luo, John Zhang, Fei Xia

Research output: Contribution to journalArticle

Abstract

The reaction of diazo compounds with transition-metal carbenes is an efficient way to achieve the functionalization of chemical bonds in organic molecules, especially for the C-H and O-H bonds. However, the selective mechanisms of C-H and O-H bond insertions by various metal carbenes such as Rh and Cu complexes are not quite clear. In this work, we performed a comprehensively theoretical investigation of the phenol C-H and O-H bonds inserted by Rh and Cu carbenes by using DFT calculations. The calculated results reveal that the nucleophilic additions of phenols to the Rh and Cu carbenes in the C-H bond insertions are the rate-determining steps of whole reactions, which are higher than the barriers in the O-H insertions. In the process of intramolecular [1,3]-H transfer, the Rh and Cu ligands in their carbenes tend to dissociate into solution rather than the intramolecular migration due to their weak metal-carbon bonds. A deeply theoretical analysis of the electronic structures of Rh, Cu, and Au carbenes as well as their complexes elucidated their differences in the chemoselectivity of C-H and O-H insertion products, which agrees with the experimental observations well.

Original languageEnglish (US)
Pages (from-to)6485-6492
Number of pages8
JournalJournal of Physical Chemistry A
Volume120
Issue number32
DOIs
StatePublished - Aug 18 2016

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Phenols
carbenes
Discrete Fourier transforms
phenols
Transition metals
insertion
transition metals
Metals
Chemical bonds
chemical bonds
Phenol
metals
Electronic structure
carbene
Carbon
electronic structure
Ligands
ligands
Molecules
carbon

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

DFT Calculations on the Mechanism of Transition-Metal-Catalyzed Reaction of Diazo Compounds with Phenols : O-H Insertion versus C-H Insertion. / Liu, Yuan; Luo, Zhoujie; Zhang, John; Xia, Fei.

In: Journal of Physical Chemistry A, Vol. 120, No. 32, 18.08.2016, p. 6485-6492.

Research output: Contribution to journalArticle

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