1,2-(Benz)Azaphospholes: A Slow Beginning to a Bright Future

Redox-active carborane clusters in bond activation chemistry and ligand design

“…1 Currently, significant attention is focused on the conceptually similar metal-free redox bond activation transformations inspired by recent discoveries. [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] It has been demonstrated that the electronic structure (i.e., energy levels of frontier orbitals) of main group compounds can be significantly altered by changes in the substitution patterns or by the introduction of geometric constraints. As one prominent example, cyclic (alkyl)(amino)carbenes (CAACs), which possess both higherenergy HOMOs and lower-energy LUMOs than N-heterocyclic carbenes (NHCs), resulting in significantly greater s-donation and p-acceptance, participate in the activation of strong H-H, B-H, Si-H, and N-H bonds through oxidative addition at the carbene center.…”

“…Currently, significant attention is focused on the conceptually similar metal-free redox bond activation transformations inspired by recent discoveries. 2–19 It has been demonstrated that the electronic structure ( i.e. , energy levels of frontier orbitals) of main group compounds can be significantly altered by changes in the substitution patterns or by the introduction of geometric constraints.…”