Chapter 15 Conjugated Systems, Orbital Symmetry, and Ultraviolet Spectroscopy 有机化学英文版教学课件（美国达拉斯社区学院） 《Organic Chemistry 5th Edition (L.G. Wade JR.)》.pptVIP

Chaper 15 Chapter 15Conjugated Systems, Orbital Symmetry, and Ultraviolet Spectroscopy Definitions Conjugated double bonds are separated by one single bond. Example: 1,3-pentadiene. Isolated double bonds are separated by two or more single bonds. 1,4-pentadiene. Cumulated double bonds are on adjacent carbons. Example: 1,2-pentadiene.  = Resonance Energy Heat of hydrogenation for trans-1,3-pentadiene is less than expected. ?H for 1-pentene is 30.0 kcal/mol and for trans-2-pentene is 27.4 kcal/mol, so expect 57.4 kcal for trans-1,3-pentadiene. Actual ?H is 53.7 kcal, so the conjugated diene is more stable. Difference, (57.4 – 53.7) 3.7 kcal/mol, is the resonance energy. = Relative Stabilities Structure of 1,3-Butadiene Most stable conformation is planar. Single bond is shorter than 1.54 ?. Electrons are delocalized over molecule. Constructing Molecular Orbitals Pi molecular orbitals are the sideways overlap of p orbitals. p orbitals have 2 lobes. Plus (+) and minus (-) indicate the opposite phases of the wave function, not electrical charge. When lobes overlap constructively, (+ and +, or - and -) a bonding MO is formed. When + and - lobes overlap, waves cancel out and a node forms; antibonding MO. = ?1 MO for 1,3-Butadiene Lowest energy. All bonding interactions. Electrons are delocalized over four nuclei.   = ?2 MO for 1,3-Butadiene 2 bonding interactions 1 antibonding interaction A bonding MO   = ?3* MO for 1,3-Butadiene Antibonding MO Empty at ground state Two nodes = ?4* MO for 1,3-Butadiene All antibonding interactions. Highest energy. Vacant at ground state.  = MO Energy Diagram Conformations of 1,3-Butadiene s-trans confor