Halogen Photoelimination from SbV Dihalide Corroles. Academic Article uri icon


  • Main-group p-block metals are ideally suited for mediating two-electron reactions because they cycle between M n and M n+2 redox states, as the one-electron state is thermodynamically unstable. Here, we report the synthesis and structure of an SbIII corrole and its SbVX2 (X = Cl, Br) congeners. SbIII sits above the corrole ring, whereas SbV resides in the corrole centroid. Electrochemistry suggests interconversion between the SbIII and SbVX2 species. TD-DFT calculations indicate a HOMO LUMO+2 parentage for excited states in the Soret spectral region that have significant antibonding character with respect to the Sb-X fragment. The photochemistry of 2 and 3 in THF is consistent with the computational results, as steady-state photolysis at wavelengths coincident with the Soret absorption of SbVX2 corrole lead to its clean conversion to the SbIII corrole. This ability to photoactivate the Sb-X bond reflects the proclivity of the pnictogens to rely on the PnIII/V couple to drive the two-electron photochemistry of M-X bond activation, an essential transformation needed to develop HX-splitting cycles.

published proceedings

  • Inorg Chem

altmetric score

  • 4.35

author list (cited authors)

  • Lemon, C. M., Hwang, S. J., Maher, A. G., Powers, D. C., & Nocera, D. G.

citation count

  • 15

complete list of authors

  • Lemon, Christopher M||Hwang, Seung Jun||Maher, Andrew G||Powers, David C||Nocera, Daniel G

publication date

  • April 2018