南京大学结构化学双语课件CH6LEC3.pptVIP

6.5 Chemical Reactions Topics 1. Frontier Orbitals Examples of Frontier Orbital Understanding Frontier Orbitals HOMO-LUMO Gaps of Some Molecules Picture of Frontier Orbitals Diels-Alder Addition Butadiene and ethylene Frontier Orbitals Butadiene and ethylene, addition reaction Frontier Orbitals Rough evaluation of molecular energies for even alternant Frontier Orbitals Rough evaluation of molecular energies for even alternant Frontier Orbitals Rough evaluation of molecular energies for even alternant Frontier Orbitals Rough evaluation of molecular energies for even alternant Frontier Orbitals Active sites in electrophilic attack, revisited Frontier Orbitals Active sites in electrophilic attack, revisited Frontier Orbitals Active sites in electrophilic attack, revisited Frontier Orbitals Active sites in electrophilic attack, revisited Frontier Orbitals Active sites in electrophilic attack, revisited Frontier Orbitals Electrocyclic reactions Electrocyclic Reactions, FOT Explanation Frontier Orbitals Theory (FOT) Electrocyclic reactions, Correlation Diagram 4l+2 Rule 6.6 Conjugated Molecules Containing Hetero-atoms Stabilization of unstable conjugated hydrocarbons Hückel Parameters for Hetroatoms List of Parameters for Different Atoms Allyl-Like Conjugated Moleculse * 1. Frontier orbitals （前线轨道） 2. Odd alternants （基交替烃） 3. Electrophilic aromatic substitution 4. Pericyclic reactions （周环反应） Benzene HOMO LUMO Butadiene HOMO LUMO Frontier Orbitals HOMO 和 LUMO 轨道（有时还包括临近的少数轨道）被称为前线轨道。它们决定分子的化学反应性。 通常，反应过程中HOMO 轨道成为电子给体，而 LUMO 则为电子受体。 HOMO 与 LUMO轨道间的能隙亦可以作为衡量分子动力学稳定性的重要依据。较大的能隙意味着较高的稳定性和较低的反应活性。 -0.004 -0.022 0.027 0.023 0.055 0.065 REPE 0.31 -0.311 0 haptalene 0.47 0 0.471 pentalene 0.89 -0.445 0.445 biphenylene 0.88 -0.400 0.477 azulene 1.22 -0.618 0.618 naphthalene 2 -1 1 benzene Gap (D/b) LUMO HOMO Molecule Reason for higher reactivity in electrophilic substitution reactions at a-sites of naphthalene. HOMO LUMO HOMO LUMO 3.56eV Questionable! To be checked! Se