Computational Investigations for Undergraduate Organic Chemistry: Modeling Markovnikov and anti-Markovnikov Reactions for the Formation of Alkyl Halides and Alcohols

Hessley, Rita K.

doi:10.1021/ed077p794

Cited by 14 publications

(11 citation statements)

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“…Electrophilic addition to alkenes is one of the most widely studied reactions. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] As is well-known, the chemistry of alkenes mainly depends on the characteristic double bond between two carbon atoms. Electrophilic addition to an alkene is characterized by its regioselectivity and reactivity.…”

Section: Introductionmentioning

confidence: 99%

“…For the better understanding and interpretation of the regiospecificity of Markovnikov reactions the electrostatic potential as well as the electron density distribution in a molecule have been emphasized by Hessley. [12] Re-Electrophilic additions of hydrogen halides to alkenes in the gas phase are investigated with a high-level ab initio method, MP2/ 6-311 + GA C H T U N G T R E N N U N G (3df,2p). Based on this, the interesting features of these reactions along the IRC routes are characterized by the molecular face (MF) theory.…”

Section: Introductionmentioning

confidence: 99%

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Insight into Markovnikov Reactions of Alkenes in Terms of Ab Initio and Molecular Face Theory

2008

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Electrophilic additions of hydrogen halides to alkenes in the gas phase are investigated with a high-level ab initio method, MP2/6-311+G(3df,2p). Based on this, the interesting features of these reactions along the IRC routes are characterized by the molecular face (MF) theory. For an alkene at the initial state, if the representative electron density (ED) encoded on the molecular face (MF) of the Markovnikov (M) carbon atom (the carbon with more hydrogen atoms) is larger than that of the anti-Markovnikov (AM) carbon atom (the carbon with fewer hydrogen atoms), the electrophilic addition reaction is predicted to proceed along the Markovnikov addition route; in the reverse situtation, the anti-Markovnikov addition route would be slightly preferred. It is then demonstrated that for a series of alkenes, the difference between activation energies of Markovnikov and anti-Markovnikov addition routes [DeltaE(#) ((M-AM))] has a good linear correlation with sign(K(ED))K(2) (ED), where K(ED) is characteristic of the electron density (ED) at the pi region in the initial state of the alkenes. Interestingly, there is a good linear correlation between our sign (K(ED))K(2) (ED) and the absolute values of difference in the core ionization energy between M and AM carbon atoms obtained by others (L. J. Saethre, T. D. Thomas, S. Svensson J. Chem. Soc. P2 1997, 2, 749.) in terms of the experimental study. In addition, the spatial dynamic changing features of the MF faces and interesting pictures of the electron transfer are clearly shown during the course of the electrophilic addition reactions. These results indicate that not only regioselectivity, but also activation energy and reactivity correlate with the pi charge distribution in the initial state of the alkenes for electrophilic addition reactions.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Insight into Markovnikov Reactions of Alkenes in Terms of Ab Initio and Molecular Face Theory

2008

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“…In addition to the mandatory experiments, students are required to design an independent computational project in consultation with the instructor. They may choose an experiment that has already been published in this journal (e.g., refs − ), design a project that is relevant to research projects they have carried out in experimental groups, or explore technical aspects of first-principles calculations. This allows students to focus on topics that are interesting to them and is relevant to their diverse backgrounds.…”

Section: Laboratory Course Setupmentioning

confidence: 99%

The Computational Design of Two-Dimensional Materials

et al. 2019

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A computational laboratory experiment investigating molecular models for hexagonal boron–carbon–nitrogen sheets (h-BCN) was developed and employed in an upper-level undergraduate chemistry course. Students used the Avogadro user interface for molecular editing and the WebMO interface for the quantum computational workflow. Density functional theory calculations were carried out to compare the electronic structures, relative energies, and other properties of mono-, di-, and tetrameric h-BCN molecular models. Experimental precursor molecules and other analogous single-layer two-dimensional (2D) materials were studied as well. These computations exemplified how electronic properties such as the band gaps of potentially useful 2D materials can be finely tuned by varying chemical structure.

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“…The addition reaction to the alkenes [24,28,[32][33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48] is one of the most widely studied objects, and it is an important method used in many industrial productions. Schematic competing electrophilic routes to alkenes are depicted in Scheme 1.…”

Section: Introductionmentioning

confidence: 99%

Insight into generalized local softness based on ABEEM‐σπ method: Electrophilic additions to alkenes

Ding

Sun

Guo

et al. 2021

J Chinese Chemical Soc

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According to the local hard-soft acidbase (HSAB) principle, the generalized local softness has been investigated based on the electrophilic reactions of H 2 O, HF, HCl and HBr to alkenes, and the effect of the softness on the chemical reactivity was studied in terms of the ab initio and atom-bond electronegativity equalization method plus σπ (ABEEM-σπ) method. Studies show that the finite difference approximation with ab initio method cannot always be used to predict the regioselectivity of the investigated reactions in terms of the local HSAB principle. But ABEEM-σπ model could well describe chemical reactivity according to the local HSAB principle. A significant characteristic of the ABEEM-σπ method is that the double bond is explicitly considered and partitioned. The square sums of differences of the local softness of the reaction center atoms, that is, Δs, or ΔS G with the generalized local softness and Δs χ with the electronegativity, have been studied on the considered electrophilic additions. Studies indicate that ΔS G can be utilized not only to predict regioselectivity rules but also to rationalize the chemical reactivity of these addition reactions, and the generalized local softness is more suitable for the investigation of chemical reactivity between two chemical species.

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Computational Investigations for Undergraduate Organic Chemistry: Modeling Markovnikov and anti-Markovnikov Reactions for the Formation of Alkyl Halides and Alcohols

Cited by 14 publications

References 0 publications

Insight into Markovnikov Reactions of Alkenes in Terms of Ab Initio and Molecular Face Theory

Insight into Markovnikov Reactions of Alkenes in Terms of Ab Initio and Molecular Face Theory

The Computational Design of Two-Dimensional Materials

Insight into generalized local softness based on ABEEM‐σπ method: Electrophilic additions to alkenes

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