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The activation strain model and molecular orbital theory.

Wolters LP, Bickelhaupt FM - Wiley Interdiscip Rev Comput Mol Sci (2015)

Bottom Line: Using these approaches, a causal relationship is revealed between the properties of the reactants and their reactivity, e.g., reaction barriers and plausible reaction mechanisms.These examples demonstrate how the methodology is applied to different research questions, how results are interpreted, and how insights into one chemical phenomenon can lead to an improved understanding of another, seemingly completely different chemical process.WIREs Comput Mol Sci 2015, 5:324-343. doi: 10.1002/wcms.1221.

View Article: PubMed Central - PubMed

Affiliation: Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling (ACMM), VU University AmsterdamAmsterdam, The Netherlands; Dipartimento di Scienze Chimiche, Università degli Studi di PadovaPadova, Italy.

ABSTRACT

The activation strain model is a powerful tool for understanding reactivity, or inertness, of molecular species. This is done by relating the relative energy of a molecular complex along the reaction energy profile to the structural rigidity of the reactants and the strength of their mutual interactions: ΔE(ζ) = ΔE strain(ζ) + ΔE int(ζ). We provide a detailed discussion of the model, and elaborate on its strong connection with molecular orbital theory. Using these approaches, a causal relationship is revealed between the properties of the reactants and their reactivity, e.g., reaction barriers and plausible reaction mechanisms. This methodology may reveal intriguing parallels between completely different types of chemical transformations. Thus, the activation strain model constitutes a unifying framework that furthers the development of cross-disciplinary concepts throughout various fields of chemistry. We illustrate the activation strain model in action with selected examples from literature. These examples demonstrate how the methodology is applied to different research questions, how results are interpreted, and how insights into one chemical phenomenon can lead to an improved understanding of another, seemingly completely different chemical process. WIREs Comput Mol Sci 2015, 5:324-343. doi: 10.1002/wcms.1221.

No MeSH data available.


Related in: MedlinePlus

Schematic substrate LUMO composition for (a) CH3CH2OH and (b) CH3CH2OH2+.
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fig12: Schematic substrate LUMO composition for (a) CH3CH2OH and (b) CH3CH2OH2+.

Mentions: There is, however, yet another reason behind this shift in preferred mechanism, caused by the different nature of the leaving groups present under both circumstances. This can be derived from a careful investigation of the electronic structure of the CH3CH2OH and CH3CH2OH2+ substrates. In Figure 12, schematic MO diagrams are shown for these substrates, constructed from the fragments CH3• and •CH2OH or •CH2OH2+.


The activation strain model and molecular orbital theory.

Wolters LP, Bickelhaupt FM - Wiley Interdiscip Rev Comput Mol Sci (2015)

Schematic substrate LUMO composition for (a) CH3CH2OH and (b) CH3CH2OH2+.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4696410&req=5

fig12: Schematic substrate LUMO composition for (a) CH3CH2OH and (b) CH3CH2OH2+.
Mentions: There is, however, yet another reason behind this shift in preferred mechanism, caused by the different nature of the leaving groups present under both circumstances. This can be derived from a careful investigation of the electronic structure of the CH3CH2OH and CH3CH2OH2+ substrates. In Figure 12, schematic MO diagrams are shown for these substrates, constructed from the fragments CH3• and •CH2OH or •CH2OH2+.

Bottom Line: Using these approaches, a causal relationship is revealed between the properties of the reactants and their reactivity, e.g., reaction barriers and plausible reaction mechanisms.These examples demonstrate how the methodology is applied to different research questions, how results are interpreted, and how insights into one chemical phenomenon can lead to an improved understanding of another, seemingly completely different chemical process.WIREs Comput Mol Sci 2015, 5:324-343. doi: 10.1002/wcms.1221.

View Article: PubMed Central - PubMed

Affiliation: Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling (ACMM), VU University AmsterdamAmsterdam, The Netherlands; Dipartimento di Scienze Chimiche, Università degli Studi di PadovaPadova, Italy.

ABSTRACT

The activation strain model is a powerful tool for understanding reactivity, or inertness, of molecular species. This is done by relating the relative energy of a molecular complex along the reaction energy profile to the structural rigidity of the reactants and the strength of their mutual interactions: ΔE(ζ) = ΔE strain(ζ) + ΔE int(ζ). We provide a detailed discussion of the model, and elaborate on its strong connection with molecular orbital theory. Using these approaches, a causal relationship is revealed between the properties of the reactants and their reactivity, e.g., reaction barriers and plausible reaction mechanisms. This methodology may reveal intriguing parallels between completely different types of chemical transformations. Thus, the activation strain model constitutes a unifying framework that furthers the development of cross-disciplinary concepts throughout various fields of chemistry. We illustrate the activation strain model in action with selected examples from literature. These examples demonstrate how the methodology is applied to different research questions, how results are interpreted, and how insights into one chemical phenomenon can lead to an improved understanding of another, seemingly completely different chemical process. WIREs Comput Mol Sci 2015, 5:324-343. doi: 10.1002/wcms.1221.

No MeSH data available.


Related in: MedlinePlus