Two T-shaped 14-electron rhodium complexes 2a and 2b, “framed” and thus stabilized by PNP pincer ligands have been synthesized. The bis(t-butyl)phosphine derived PNPtBu-rhodium 2a was isolated from pentane as the more stable cyclometalated Rh(III) hydrido complex and found to be in equilibrium with the T-shaped 14e-Rh(I) complex 2aT which itself could be directly crystallized upon change of the solvent. The cyclometallation is suppressed using an adamantyl substituted PNPAd ligand to give …