Unexpected Molecular Structure of a Putative Rhenium‐Dioxo‐Benzocarbaporphyrin Complex. Implications for the Highest Transition Metal Valence in a Porphyrin‐Type Ligand Environment

A combination of quantum chemical calculations and synthetic studies was used to address the possibility of very high (>6) valence states of transition metals in porphyrin‐type complexes. With corrole as a supporting ligand, DFT calculations ruled out Re(VII) and Ir(VII) dioxo complexes as stable species. Attempted rhenium insertion into benzocarbaporphyrin (BCP) ligands on the other hand led to two products with different stoichiometries – Re[BCP]O and Re[BCP]O(2). To our surprise, single‐crystal structure determination of one of the complexes of the latter type indicated an Re(V)O center with a second oxygen bridging the Re−C bond. In other words, although the monooxo complexes Re[BCP]O are oxophilic, the BCP ligand cannot sustain a trans‐Re(VII)(O)(2) center. The search for metal valence states >6 in porphyrin‐type ligand environments must therefore continue.