Double C-H activation in a Rh-NHC complex leading to the isolation of a 14-electron Rh(III) complex.

The solvent-dependent interaction of ItBu with a Rh(I)-olefin complex leads to the isolation of two precursors en route to a unique double cyclometalation process. Abstraction of the chloride ligand from the resulting complex enables the isolation of a "bare" 14-electron Rh(III) complex.