When Substituents Do Not Matter: Frontier Orbitals Explain the Unusually High and Invariant Oxidation Potential in Alkoxy-, Alkyl-, and H-Substituted Iptycenes
American Chemical Society
Journal of Physical Chemistry Letters
Frontier molecular orbitals (FMOs) have played a critical role in predicting reactivity/selectivity of pericyclic reactions. Here we show that the structurally similar iptycene-based hydroquinone ether (HE), that is, MeOIpt and BOHE/BHHE, molecules have drastically different ordering of bisallylic and quinoidal FMOs. They are almost degenerate in BOHE/BHHE, while in MeOIpt, the bisallylic orbital lies far below the quinoidal HOMO. Oxidation of BOHE/BHHE induces coplanarization of the methoxy group and destabilizes the bisallylic HOMO, leading to a relatively low oxidation potential. In MeOIpt, considerable energy must be invested in coplanarization of the methoxy group to bring about orbital swapping, resulting in an oxidation potential higher than that in structurally similar BOHE/BHHE. As the quinoidal HOMO density does not extend to the substituent-bearing carbon in H-, alkyl-, and alkoxy-substituted iptycenes, their redox potentials remain invariant. This case study involving a simple visual inspection of the nodal arrangement as well as energetics of the FMOs and Walsh analysis could serve as a tool for the design of organic molecules with a desired redox potential.
Ivanov, Maxim V.; Wang, Denan; Wadumethrige, Shriya; and Rathore, Rajendra, "When Substituents Do Not Matter: Frontier Orbitals Explain the Unusually High and Invariant Oxidation Potential in Alkoxy-, Alkyl-, and H-Substituted Iptycenes" (2017). Chemistry Faculty Research and Publications. 886.
ADA Accessible Version
Accepted version. Journal of Physical Chemistry Letters, Vol. 8, No. 17 (September 7, 2017): 4226-4230. DOI. © 2019 American Chemical Society. Used with permission.