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Nazarov Cyclization

Nazarov Cyclization. Photochromic materials. HSAB Principle. Atomic (ionic) radius Effective nuclear charge Electron negativity Polarizability Oxidizability Frontier Molecular Orbitals. HSAB Principle. Hard nucleophiles have a low-energy HOMO and usually have a negative charge.

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Nazarov Cyclization

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  1. Nazarov Cyclization

  2. Photochromic materials

  3. HSAB Principle • Atomic (ionic) radius • Effective nuclear charge • Electron negativity • Polarizability • Oxidizability • Frontier Molecular Orbitals

  4. HSAB Principle • Hard nucleophiles have a low-energy HOMO and usually have a negative charge. • Soft nucleophiles have a high-energy HOMO but do not necessarily have a negative charge. • Hard electrophiles have a high-energy LUMO and usually have a positive charge. • Soft electrophiles have a low-energy LUMO but do not necessarily have a positive charge. • A hard-hard reaction is fast because of a large Coulombic attraction. • A soft-soft reaction is fast because of a large interaction between the HOMO of the nucleophile and the LUMO of the electrophile. • The larger the coefficient in the appropriate frontier orbital (of the atomic orbital at the reaction centre), the softer the reagent.

  5. Some hard and soft acids (electrophiles) and bases (nucleophiles)

  6. Frontier Molecular Orbital Theory As two molecules collide, three major forces operate: • The occupied orbitals of one repel the occupied orbitals of the other. • Any positive charge on one attracts any negative charge on the other (and repels any positive). • The occupied orbitals (especially the HOMOs) of each interact with the unoccupied orbitals (especially the LUMOs) of the other, causing an attraction between the molecules. Hoffmann, Roald; Woodward, R. B.. Science 1970, 167, 825-31. Woodward, Robert B.; Hoffmann, Roald. Angew. Chem. Int. Edit. 1969, 8, 781-853.

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