Density Functional Theoritical Studies on Catalytic C-H Activation Reaction: Problem of Truncated Model†

doi:10.7503/cjcu20140246

Abstract

Abstract:

Density functional theory method was employed to simulate a Rh(PPh₃)₃Cl catalyzed C-H activation/C-C cross-coupling reaction, in which three typical processes, namely, C-H activation, migratory insertion and reductive elimination, were characterized. The obtained results show that the rate-determining step is migratory insertion with the free-energy barrier of 108.3 kJ/mol. In order to test the validation of truncated models, two small catalysts Rh(PMe₃)₃Cl and Rh(PH₃)₃Cl were also used to study the same coupling reaction. Our calculations suggested that truncated models led to misunderstanding of reaction mechanism and free-energy changes, especially for migratory insertion process, since the steric effect and entropic contribution play a great role on these types of reactions.

Key words: Density function theory, Rh-catalyst, C-H activation, C-C coupling, Truncated model

CLC Number:

O641

TrendMD:

ZHANG Lei, XU Zengping, YU Haoyu, FANG Decai. Density Functional Theoritical Studies on Catalytic C-H Activation Reaction: Problem of Truncated Model^†[J]. Chem. J. Chinese Universities, 2014, 35(6): 1241.

Figures/Tables 6

Fig.1 Catalytic C-H activation/C-C cross-coupling reaction between imines and olefins

Fig.2 General representation of the entire catalytic cycle

Fig.3 3D-structures of some selected stationary points along reaction pathThe PPh3 ligands and the substrate Bn group are not shown completely for simplicity.

Fig.4 Free-energy profile for the entire catalytic cycleThe free-energies in parentheses are derived from the default gas-phase translational entropies in Gaussian 09 package.

Fig.5 Changes of Rh-P bond-lengths(nm) and some energetic terms(kJ/mol) upon the dissociation

Fig.6 Comparison of free-energy profiles among three calculation models

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