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Wolters LP, Bickelhaupt FM. Selective C-H and C-C Bond Activation: Electronic Regimes as a Tool for Designing d(10) MLn Catalysts. Chem Asian J. 2015;10(10):2272-82doi: 10.1002/asia.201500368.
Wolters, L. P., & Bickelhaupt, F. M. (2015). Selective C-H and C-C Bond Activation: Electronic Regimes as a Tool for Designing d(10) MLn Catalysts. Chemistry, an Asian journal, 10(10), 2272-82. https://doi.org/10.1002/asia.201500368
Wolters, Lando P, and Bickelhaupt, F Matthias. "Selective C-H and C-C Bond Activation: Electronic Regimes as a Tool for Designing d(10) MLn Catalysts." Chemistry, an Asian journal vol. 10,10 (2015): 2272-82. doi: https://doi.org/10.1002/asia.201500368
Wolters LP, Bickelhaupt FM. Selective C-H and C-C Bond Activation: Electronic Regimes as a Tool for Designing d(10) MLn Catalysts. Chem Asian J. 2015 Oct;10(10):2272-82. doi: 10.1002/asia.201500368. Epub 2015 Jul 28. PMID: 26218844.
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Chem Asian J. 2015 Oct;10(10):2272-82. doi: 10.1002/asia.201500368. Epub 2015 Jul 28.

Selective C-H and C-C Bond Activation: Electronic Regimes as a Tool for Designing d(10) MLn Catalysts.

Chemistry, an Asian journal

Lando P Wolters, F Matthias Bickelhaupt

Affiliations

  1. Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling, VU University, De?Boelelaan?1083, 1081 HV, Amsterdam, The Netherlands.
  2. Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling, VU University, De?Boelelaan?1083, 1081 HV, Amsterdam, The Netherlands. [email protected].
  3. Radboud University Nijmegen, Institute for Molecules and Materials, Heyendaalseweg?135, 6525 AJ, Nijmegen, The Netherlands. [email protected].

PMID: 26218844 DOI: 10.1002/asia.201500368

Abstract

We wish to understand how a transition-metal catalyst can be rationally designed so as to selectively activate one particular bond in a substrate, herein, C-H and C-C bonds in ethane. To this end, we quantum chemically analyzed the activity and selectivity of a large series of model catalysts towards ethane and, for comparison, methane, by using the activation strain model and quantitative molecular orbital theory. The model catalysts comprise d(10) MLn complexes with coordination numbers n=0, 1, and 2; metal centers M=Co(-), Rh(-), Ir(-), Ni, Pd, Pt, Cu(+), Ag(+), and Au(+); and ligands L=NH3, PH3, and CO. Our analyses reveal that rather subtle electronic differences between bonds can be exploited to induce a lower barrier for activating one or the other, depending, among other factors, on the catalysts electronic regime (i.e., s-regime versus d-regime catalysts). Interestingly, the concepts and design principles emerging from this work can also be applied to the more challenging problem of differentiating between activation of the C-H bonds in ethane versus those in methane.

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Keywords: C−H activation; activation strain model; catalyst design; molecular orbital theory; transition metals

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