Topological aspects of chemical reactivity. Destiny of electron pairs in allowed and forbidden pericyclic reactions

2017 ◽  
Vol 30 (12) ◽  
pp. e3706 ◽  
Author(s):  
Robert Ponec
Keyword(s):  
Chemical Reactivity ◽  
Pericyclic Reactions ◽  
Electron Pairs

Similarity approach to chemical reactivity. Torquoselectivity in pericyclic reactions

1996 ◽  
Vol 20 (2) ◽  
pp. 301-310 ◽  
Author(s):  
Robert Ponec ◽  
Gleb Yuzhakov ◽  
Jaroslav Pecka
Keyword(s):  
Chemical Reactivity ◽  
Pericyclic Reactions

Topological aspects of chemical reactivity. On the possible use of similarity index in characterizing the transition state structure in concerted pericyclic reactions

1987 ◽  
Vol 52 (6) ◽  
pp. 1375-1385
Author(s):  
Robert Ponec
Keyword(s):  
Transition State ◽  
Chemical Reactivity ◽  
Transition States ◽  
Similarity Index ◽  
Pericyclic Reactions ◽  
State Structure ◽  
Transition State Structure ◽  
Topological Similarity

The use of the topological similarity index as a simple means for classification and characterization of the structure of the transition states in concerted pericyclic reactions is discussed. The suggested formulation makes it possible to bring a quantitative aspects into the empirical Dewar's classification of transition states in terms of aromaticity and/or antiaromaticity.

Topological aspects of chemical reactivity. A simple method for estimating the activation energies in pericyclic reactions

1986 ◽  
Vol 51 (1) ◽  
pp. 175-187
Author(s):  
Robert Ponec
Keyword(s):  
Quantum Chemical ◽  
Chemical Reactivity ◽  
Activation Energies ◽  
Topological Model ◽  
Pericyclic Reactions ◽  
Simple Method ◽  
Proposed Model ◽  
Designed Synthesis

A simple topological model allowing to estimate the activation energies in thermally initiated pericyclic reactions is proposed. The formalism of the model is closely connected with the recently formulated overlap determinant method. Due to its simplicity the proposed model is especially convenient for the semiquantitative estimate of the reactivity, e.g. in computer designed synthesis where even the simplest quantum chemical procedures are still too time consuming.

scholarly journals A Common Selection Rule for Organic Reactions in Terms of Signs of Direct and Indirect Interorbital Interactions

2009 ◽  
Vol 64 (1-2) ◽  
pp. 132-148 ◽  
Author(s):  
Viktorija Gineityte
Keyword(s):  
Power Series ◽  
Total Energy ◽  
Selection Rule ◽  
Chemical Reactivity ◽  
Organic Reactions ◽  
Chemical Bonds ◽  
Pericyclic Reactions ◽  
Order Energy ◽  
Phenyl Rings ◽  
Substituted Alkanes

The semilocalized approach to chemical reactivity suggested recently is overviewed with respect to both theory and applications. The principal attention is paid to formulation of a common selection rule for organic reactions and to demonstration of its validity to various heterolytic (i. e. nucleophilic and electrophilic) and pericyclic processes. The total energy of the whole reacting system (E) is represented in this approach in the form of power series with respect to all interfragmental interactions (fragments coincide with individual chemical bonds, phenyl rings, etc.). For any reaction, a certain decisive k-th-order energy correction E(k) may be revealed, the sign of which depends on the actual way of the process. The allowed and forbidden reactions are then defined as those described by negative (stabilizing) and positive (destabilizing) corrections E(k), respectively. The condition which ensures the negative sign of E(k) resolves itself into a universal requirement of coinciding signs of the principal direct and indirect interactions of basis orbitals localized on separate fragments (e. g. bond orbitals). This result forms the basis for the above-mentioned selection rule. Allowed (forbidden) ways of heterolytic reactions are exemplified by the back (frontal) attack of a nucleophile upon a substituted alkane in the SN2 process, the meta (ortho, para) attacks of electrophile upon the pyridine molecule, the addition of electrophile to the Cβ (Cα ) atom of a donor-containing derivative of ethene (D-CαH=Cβ H2), the trans (cis)-β -elimination processes of substituted alkanes, etc. Application of the same rule to pericyclic reactions is demonstrated to yield predictions coinciding with those of other approaches including the famous Woodward-Hoffmann rule.

Geodesic Formulation of the Least Motion Principle in Chemical Reactivity

1992 ◽  
Vol 57 (2) ◽  
pp. 232-240 ◽  
Author(s):  
Martin Strnad ◽  
Robert Ponec
Keyword(s):  
Mathematical Model ◽  
Hilbert Space ◽  
Structural Changes ◽  
Chemical Reactivity ◽  
The State ◽  
Pericyclic Reactions ◽  
Electron States ◽  
Intuitive Criterion

In this study an attempt is presented at the quantitative formulation of the old intuitive criterion for the characterization of chemical reactivity known as the principle of the least motion. The proposed formulation originates from the abstract mathematical model, within the framework of which the criterion of minimal structural changes is realized by the requirement of minimal changes of the state vectors in the Hilbert space of electron states. The presented approach is demonstrated on the practical example of pericyclic reactions for which its results correctly reproduce the conclusions of Woodward-Hoffmann rules.

Topological methods of quantum chemistry for a study of chemical reactivity

1980 ◽  
Vol 45 (9) ◽  
pp. 2452-2462 ◽  
Author(s):  
Jiří Pancíř
Keyword(s):  
Electronic Structures ◽  
Chemical Reactivity ◽  
Average Error ◽  
Medium Size ◽  
Electron Pairs ◽  
Hartree Fock ◽  
Structural Formulas ◽  
Quantum Chemical Model ◽  
Core Electrons ◽  
The One

In this paper all approximations are discussed which lead to a quantum chemical model which is adequate for structural formulas known in classical organic chemistry. Neglect of the energy differences caused by changes of valence and dihedral angles, i.e. neglect of all nonbonding interactions, leads to the separation of the Hartree-Fock matrix in blocks of core electrons, nonbonding electron pairs, two center blocks of σ-bonds and delocalized π-electronic structures. Such a procedure can be formulated at all levels of sophistication - from the one electron approximation to the MC-SCF method. Even on the one electron level, the average error in heats of atomization (35.9 kJ/mol) is lower than that of the more complicated geometrical methods MINDO/3 (52.1 kJ/mol) and MNDO (39.6 kJ/mol). The procedure suggested is about two orders of magnitude more efficient than geometrical ones of the same level and can be, therefore, used for a study of reaction mechanisms of medium size systems (30-50 atoms) without large expense.

Topological aspects of chemical reactivity. Catalytic reactions

1986 ◽  
Vol 51 (9) ◽  
pp. 1843-1855 ◽  
Author(s):  
Robert Ponec
Keyword(s):  
Transition Metal ◽  
Detailed Analysis ◽  
Chemical Reactivity ◽  
Metal Catalysts ◽  
Transition Metal Catalysts ◽  
Catalytic Reactions ◽  
Pericyclic Reactions

Recently proposed overlap determinant method is applied to the description of reactions induced by the presence of the transition metal catalysts. The use of this technique is demonstrated on a detailed analysis of a number of examples of thermally forbidden pericyclic reactions in which the interaction with the catalyst removes the symmetry restrictions imposed by Woodward-Hoffmann rules.

Similarity Approach to Chemical Reactivity. Substituent Effect in Pericyclic Reactions

1993 ◽  
Vol 58 (1) ◽  
pp. 11-23 ◽  
Author(s):  
Robert Ponec
Keyword(s):  
Substituent Effect ◽  
Chemical Reactivity ◽  
Theoretical Data ◽  
Systematic Investigation ◽  
Pericyclic Reactions ◽  
Basic Features

The recently introduced similarity approach to chemical reactivity was applied to the systematic investigation of the substituent effect on pericyclic reactivity. The agreement of the resulting predictions with available experimental or theoretical data confirms that the basic features of the substituent effect are correctly reproduced by the model.

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