energy for the analogous β-Cl elimination is only slightly destabilizing which results
in the much lower activation barrier computed for this transformation.
4 Summary and Outlook
By means of selected representative examples, we have presented in this chapter an
overview of the good performance of the combination of the ASM and EDA
(NOCV) methods in aiding a detailed and quantitative understanding of the reactivity in transition metal-mediated transformations. The selected representative recent
applications span from fundamental oxidative addition or β-elimination reactions to
more intricate gold(I)-catalyzed hydroarylation or hydroamination reactions, therefore covering a good number of different processes in organometallic chemistry.
This alternative method, which is rooted on accurate quantum chemical calculations
and is fully applicable to any chemical transformation (including intramolecular
processes), allows us to get a deeper, quantitative insight into the physical factors
governing the barrier heights and associated reactivity trends in chemistry. Despite
its relatively recent introduction, the ASM-EDA (NOCV) is nowadays a consolidated methodology which has greatly contributed to our current understanding of
fundamental processes in chemistry. In addition, the insight gained by this methodology can be used for the so much desired rational design of more efficient or entirely
novel transformations, particularly in organometallic chemistry.
Acknowledgments Financial support was provided by the Spanish Ministerio de Economía y
Competitividad (MINECO) and FEDER (Grants CTQ2016-78205-P and CTQ2016-81797REDC).
References
1. Fernández I, Bickelhaupt FM (2014) The activation strain model and molecular orbital theory:
understanding and designing chemical reactions. Chem Soc Rev 43:4953–4967
2. Wolters LP, Bickelhaupt FM (2015) The activation strain model and molecular orbital theory.
WIREs Comput Mol Sci 5:324–343
3. Bickelhaupt FM, Houk KN (2017) Analyzing reaction rates with the distortion/interactionactivation strain model. Angew Chem Int Ed 56:10070–10086
4. Fernández I (2014) Understanding trends in reaction barriers. In: Pignataro B (ed) Discovering
the future of molecular sciences. Wiley, Weinheim, pp 165–187
5. Bickelhaupt FM, Baerends EJ (2000) Kohn-Sham density functional theory: predicting and
understanding chemistry. In: Lopkowitz KB, Boyd DB (eds) Reviews in computational chemistry, vol 15. Wiley, New York, pp 1–86
6. von Hopffgarten M, Frenking G (2012) Energy decomposition analysis. WIREs Comput Mol
Sci 2:43–62
7. Frenking G, Bickelhaupt FM (2014) The EDA perspective of chemical bonding. In:
Frenking G, Shaik S (eds) The chemical bond: fundamental aspects of chemical bonding.
Wiley, Weinheim, pp 121–157
A Quantitative Approach to Understanding Reactivity in Organometallic Chemistry
127
in the much lower activation barrier computed for this transformation.
4 Summary and Outlook
By means of selected representative examples, we have presented in this chapter an
overview of the good performance of the combination of the ASM and EDA
(NOCV) methods in aiding a detailed and quantitative understanding of the reactivity in transition metal-mediated transformations. The selected representative recent
applications span from fundamental oxidative addition or β-elimination reactions to
more intricate gold(I)-catalyzed hydroarylation or hydroamination reactions, therefore covering a good number of different processes in organometallic chemistry.
This alternative method, which is rooted on accurate quantum chemical calculations
and is fully applicable to any chemical transformation (including intramolecular
processes), allows us to get a deeper, quantitative insight into the physical factors
governing the barrier heights and associated reactivity trends in chemistry. Despite
its relatively recent introduction, the ASM-EDA (NOCV) is nowadays a consolidated methodology which has greatly contributed to our current understanding of
fundamental processes in chemistry. In addition, the insight gained by this methodology can be used for the so much desired rational design of more efficient or entirely
novel transformations, particularly in organometallic chemistry.
Acknowledgments Financial support was provided by the Spanish Ministerio de Economía y
Competitividad (MINECO) and FEDER (Grants CTQ2016-78205-P and CTQ2016-81797REDC).
References
1. Fernández I, Bickelhaupt FM (2014) The activation strain model and molecular orbital theory:
understanding and designing chemical reactions. Chem Soc Rev 43:4953–4967
2. Wolters LP, Bickelhaupt FM (2015) The activation strain model and molecular orbital theory.
WIREs Comput Mol Sci 5:324–343
3. Bickelhaupt FM, Houk KN (2017) Analyzing reaction rates with the distortion/interactionactivation strain model. Angew Chem Int Ed 56:10070–10086
4. Fernández I (2014) Understanding trends in reaction barriers. In: Pignataro B (ed) Discovering
the future of molecular sciences. Wiley, Weinheim, pp 165–187
5. Bickelhaupt FM, Baerends EJ (2000) Kohn-Sham density functional theory: predicting and
understanding chemistry. In: Lopkowitz KB, Boyd DB (eds) Reviews in computational chemistry, vol 15. Wiley, New York, pp 1–86
6. von Hopffgarten M, Frenking G (2012) Energy decomposition analysis. WIREs Comput Mol
Sci 2:43–62
7. Frenking G, Bickelhaupt FM (2014) The EDA perspective of chemical bonding. In:
Frenking G, Shaik S (eds) The chemical bond: fundamental aspects of chemical bonding.
Wiley, Weinheim, pp 121–157
A Quantitative Approach to Understanding Reactivity in Organometallic Chemistry
127