Symmetry and topology in chemical reactivity / Pieter E. Schipper.

Format:

Book

Author/Creator:

Schipper, Pieter E.

Language:

English

Subjects (All):

Reactivity (Chemistry).

Symmetry (Physics).

Physical Description:

1 online resource (284 p.)

Place of Publication:

Singapore ; River Edge, N.J. : World Scientific, c1994.

Language Note:

English

Summary:

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 sh

Contents:

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.

Notes:

Description based upon print version of record.

Includes bibliographical references and index.

ISBN:

9789814317160

9814317160