Symmetry and topology in chemical reactivity /
Schipper, Pieter E.
Symmetry and topology in chemical reactivity / Pieter E. Schipper. - Singapore ; River Edge, N.J. : World Scientific Pub. Co., c1994. - 1 online resource (xii, 272 p.) : ill.
Includes bibliographical references and index.
1. Chemical reactivity. 1.1. Introduction. 1.2. Geometric and electronic models. 1.3. The reaction model. 1.4. References -- 2. Reaction paths. 2.1. Molecular wave functions. 2.2. Potential energy surfaces (PES). 2.3. Normal coordinates. 2.4. Time dependent structural change. 2.5. Reaction paths: classical considerations. 2.6. Reaction paths: electronic considerations. 2.7. Vibronic integrals. 2.8. References -- 3. Spatial symmetry. 3.1. Introduction. 3.2. The point groups. 3.3. Constraints and projectors. 3.4. Vibronic integrals. 3.5. References -- 4. Structure symmetry. 4.1. Introduction. 4.2. Structure notation. 4.3. Relationships between structures. 4.4. Structure symmetry operations 4.5. Symmetry changes. 4.6. Changes along a reaction path. 4.7. Synchronicity and Q*-models. 4.8. References -- 5. CSR procedure. 5.1. The MX[symbol] rearrangement. 5.2. The double exchange mechanism. 5.3. Stage 1. The conserved group. 5.4. Stage 2. The reaction coordinate. 5.5. Stage 3. The transition state 5.6. Stage 4. Path multiplicity 5.7. Forbidden paths. 5.8. The single exchange mechanism 5.9. Summary. 5.10. References -- 6. CSR applications. 6.1. Introduction. 6.2. Metal-ligand substitution. 6.3. Symmetry lowering: template symmetry. 6.4. A chiral rearrangement. 6.5. Electrocyclic additions. 6.6. Diels-Alder additions. 6.7. Aliphatic substitution. 6.8. References -- 7. Formal electronic control. 7.1. Introduction. 7.2. General orbital theory. 7.3. The natural representation and FC-partitioning. 7.4. The vibronic potential. 7.5. The SGF potential. 7.6. Stability of partitioning. 7.7. Simpler group representations. 7.8. References -- 8. Practical QSR procedure. 8.1. Introduction. 8.2. Theoretical background I. 8.3. QSR stage 1: aliphatic substitution. 8.4. Theoretical background II. 8.5. QSR stage 2(a): aliphatic substitution. 8.6. Theoretical background III. 8.7. QSR stage 2(b): aliphatic substitution. 8.8. QSR stage 3: aliphatic substitution. 8.9. References -- 9. The CPMO potential. 9.1. Introduction. 9.2. Formulation of the CPMO potential. 9.3. Pericyclic additions. 9.4. Butadiene cyclization. 9.5. Large polyenes. 9.6. Photochemical additions. 9.7. Summary. 9.8. References -- 10. Additions. 10.1. Introduction. 10.2. Addition reactions. 10.3. Sigma mediators. 10.4. Direct additions. 10.5. Weakly mediated additions. 10.6. Diels-Alder additions. 10.7. Chiral additions. 10.8. References -- 11. Inorganic rearrangements. 11.1. Introduction. 11.2. The BeH[symbol] inversion. 11.3. The metal-ligand potential. 11.4. Evolution of the metal states. 11.5. Square planar substitution. 11.6. Reference -- 12. Substitutions. 12.1. Introduction. 12.2. Reaction discrimination. 12.3. Aromatic substitution: benzene. 12.4. The QSR analysis: benzene. 12.5. Naphthalene substitution. 12.6. References.
This well-illustrated book develops, using only the ideas of basic quantum chemistry (e.g. perturbation and symmetry theory), a fundamental conceptual and theoretical framework for chemical reactivity. By feeding the role of symmetry and chemical group topology directly into the development, the analysis generates and explains the successful features of simpler reactivity theories (e.g. frontier orbital theory, the isolobal concept, PMO theory, the Woodward-Hoffmann rules), as well as defines their limitations. The unifying construct is that of a group-resolved correlation diagram, which is shown to represent the formal quantization of the electron arrow, replacing the concept of classical point electrons moving between groups with the concept of quantum electron matter waves which evolve with the evolving nuclear and chemical group structure. The use of the concept of chemical groups (functional group system, substituents, solvents) is central to the development, localising the evolutionary electrons within the functional groups and leading to an isolation and analytic definition of substituent and solvent (catalytic) effects as explicit functions of the reaction coordinate. Each archetypical reaction family is represented by fully-worked examples: viz. aliphatic nucleophilic substitution, aromatic electrophilic substitution, inorganic rearrangements, electrocyclic additions, Diels-Alder additions and addition stages in chiral reactions.
Electronic reproduction.
Singapore :
World Scientific Publishing Co.,
1994.
System requirements: Adobe Acrobat Reader.
Mode of access: World Wide Web.
9789814317160
Reactivity (Chemistry)
Symmetry (Physics)
Electronic books.
541.394
Symmetry and topology in chemical reactivity / Pieter E. Schipper. - Singapore ; River Edge, N.J. : World Scientific Pub. Co., c1994. - 1 online resource (xii, 272 p.) : ill.
Includes bibliographical references and index.
1. Chemical reactivity. 1.1. Introduction. 1.2. Geometric and electronic models. 1.3. The reaction model. 1.4. References -- 2. Reaction paths. 2.1. Molecular wave functions. 2.2. Potential energy surfaces (PES). 2.3. Normal coordinates. 2.4. Time dependent structural change. 2.5. Reaction paths: classical considerations. 2.6. Reaction paths: electronic considerations. 2.7. Vibronic integrals. 2.8. References -- 3. Spatial symmetry. 3.1. Introduction. 3.2. The point groups. 3.3. Constraints and projectors. 3.4. Vibronic integrals. 3.5. References -- 4. Structure symmetry. 4.1. Introduction. 4.2. Structure notation. 4.3. Relationships between structures. 4.4. Structure symmetry operations 4.5. Symmetry changes. 4.6. Changes along a reaction path. 4.7. Synchronicity and Q*-models. 4.8. References -- 5. CSR procedure. 5.1. The MX[symbol] rearrangement. 5.2. The double exchange mechanism. 5.3. Stage 1. The conserved group. 5.4. Stage 2. The reaction coordinate. 5.5. Stage 3. The transition state 5.6. Stage 4. Path multiplicity 5.7. Forbidden paths. 5.8. The single exchange mechanism 5.9. Summary. 5.10. References -- 6. CSR applications. 6.1. Introduction. 6.2. Metal-ligand substitution. 6.3. Symmetry lowering: template symmetry. 6.4. A chiral rearrangement. 6.5. Electrocyclic additions. 6.6. Diels-Alder additions. 6.7. Aliphatic substitution. 6.8. References -- 7. Formal electronic control. 7.1. Introduction. 7.2. General orbital theory. 7.3. The natural representation and FC-partitioning. 7.4. The vibronic potential. 7.5. The SGF potential. 7.6. Stability of partitioning. 7.7. Simpler group representations. 7.8. References -- 8. Practical QSR procedure. 8.1. Introduction. 8.2. Theoretical background I. 8.3. QSR stage 1: aliphatic substitution. 8.4. Theoretical background II. 8.5. QSR stage 2(a): aliphatic substitution. 8.6. Theoretical background III. 8.7. QSR stage 2(b): aliphatic substitution. 8.8. QSR stage 3: aliphatic substitution. 8.9. References -- 9. The CPMO potential. 9.1. Introduction. 9.2. Formulation of the CPMO potential. 9.3. Pericyclic additions. 9.4. Butadiene cyclization. 9.5. Large polyenes. 9.6. Photochemical additions. 9.7. Summary. 9.8. References -- 10. Additions. 10.1. Introduction. 10.2. Addition reactions. 10.3. Sigma mediators. 10.4. Direct additions. 10.5. Weakly mediated additions. 10.6. Diels-Alder additions. 10.7. Chiral additions. 10.8. References -- 11. Inorganic rearrangements. 11.1. Introduction. 11.2. The BeH[symbol] inversion. 11.3. The metal-ligand potential. 11.4. Evolution of the metal states. 11.5. Square planar substitution. 11.6. Reference -- 12. Substitutions. 12.1. Introduction. 12.2. Reaction discrimination. 12.3. Aromatic substitution: benzene. 12.4. The QSR analysis: benzene. 12.5. Naphthalene substitution. 12.6. References.
This well-illustrated book develops, using only the ideas of basic quantum chemistry (e.g. perturbation and symmetry theory), a fundamental conceptual and theoretical framework for chemical reactivity. By feeding the role of symmetry and chemical group topology directly into the development, the analysis generates and explains the successful features of simpler reactivity theories (e.g. frontier orbital theory, the isolobal concept, PMO theory, the Woodward-Hoffmann rules), as well as defines their limitations. The unifying construct is that of a group-resolved correlation diagram, which is shown to represent the formal quantization of the electron arrow, replacing the concept of classical point electrons moving between groups with the concept of quantum electron matter waves which evolve with the evolving nuclear and chemical group structure. The use of the concept of chemical groups (functional group system, substituents, solvents) is central to the development, localising the evolutionary electrons within the functional groups and leading to an isolation and analytic definition of substituent and solvent (catalytic) effects as explicit functions of the reaction coordinate. Each archetypical reaction family is represented by fully-worked examples: viz. aliphatic nucleophilic substitution, aromatic electrophilic substitution, inorganic rearrangements, electrocyclic additions, Diels-Alder additions and addition stages in chiral reactions.
Electronic reproduction.
Singapore :
World Scientific Publishing Co.,
1994.
System requirements: Adobe Acrobat Reader.
Mode of access: World Wide Web.
9789814317160
Reactivity (Chemistry)
Symmetry (Physics)
Electronic books.
541.394