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Chass GA, O'Brien CJ, Hadei N, et al. Density functional theory investigation of the alkyl-alkyl Negishi cross-coupling reaction catalyzed by N-heterocyclic carbene (NHC)-Pd complexes. Chemistry. 2009;15(17):4281-8doi: 10.1002/chem.200900042.
Chass, G. A., O'Brien, C. J., Hadei, N., Kantchev, E. A., Mu, W. H., Fang, D. C., Hopkinson, A. C., Csizmadia, I. G., & Organ, M. G. (2009). Density functional theory investigation of the alkyl-alkyl Negishi cross-coupling reaction catalyzed by N-heterocyclic carbene (NHC)-Pd complexes. Chemistry (Weinheim an der Bergstrasse, Germany), 15(17), 4281-8. https://doi.org/10.1002/chem.200900042
Chass, Gregory A, et al. "Density functional theory investigation of the alkyl-alkyl Negishi cross-coupling reaction catalyzed by N-heterocyclic carbene (NHC)-Pd complexes." Chemistry (Weinheim an der Bergstrasse, Germany) vol. 15,17 (2009): 4281-8. doi: https://doi.org/10.1002/chem.200900042
Chass GA, O'Brien CJ, Hadei N, Kantchev EA, Mu WH, Fang DC, Hopkinson AC, Csizmadia IG, Organ MG. Density functional theory investigation of the alkyl-alkyl Negishi cross-coupling reaction catalyzed by N-heterocyclic carbene (NHC)-Pd complexes. Chemistry. 2009;15(17):4281-8. doi: 10.1002/chem.200900042. PMID: 19288489.
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Chemistry. 2009;15(17):4281-8. doi: 10.1002/chem.200900042.

Density functional theory investigation of the alkyl-alkyl Negishi cross-coupling reaction catalyzed by N-heterocyclic carbene (NHC)-Pd complexes.

Chemistry (Weinheim an der Bergstrasse, Germany)

Gregory A Chass, Christopher J O'Brien, Niloufar Hadei, Eric Assen B Kantchev, Wei-Hua Mu, De-Cai Fang, Alan C Hopkinson, Imre G Csizmadia, Michael G Organ

Affiliations

  1. School of Chemistry, University of Wales, Bangor, LL57 2UW, UK. [email protected]

PMID: 19288489 DOI: 10.1002/chem.200900042

Abstract

A novel mechanism is proposed for the Pd-1,3-(2,6-diisopropylphenyl)imidazolyl-2-ylidene (1) catalyzed Negishi reaction. DFT computations supported by atoms-in-molecules (AIM) analyses of non-truncated models show that a "steric wall" created by the N-substituent on the ligand guides reactants to and from the Pd center. Notably, transmetalation and not oxidative addition is found to be rate-limiting. Additionally, a key Pd-Zn interaction (approximately = 2.4 A, rho(b) approximately = 0.0600 au) is identified in the mechanism. This interaction persists beyond reductive elimination and, in combination with the ligand, facilitates reductive elimination by creating a highly sterically crowded environment in the coordination sphere of the Pd center.

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