Rhenium Corrole Dimers: Electrochemical Insights into the Nature of the Metal–Metal Quadruple Bond

[Image: see text] The interaction of free-base triarylcorroles with Re(2)(CO)(10) in 1,2-dichlorobenzene in the presence of 2,6-lutidine at 180 °C under strict anerobic conditions afforded approximately 10% yields of rhenium corrole dimers. The compounds exhibited diamagnetic (1)H NMR spectra consistent with a metal–metal quadruple bond with a σ(2)π(4)δ(2) orbital occupancy. One of the compounds proved amenable to single-crystal X-ray structure determination, yielding a metal–metal distance of ∼2.24 Å, essentially identical to that in triple-bonded osmium corrole dimers. On the other hand, the electrochemical properties of Re and Os corrole dimers proved to be radically different. Thus, the reduction potentials of the Re corrole dimers are some 800 mV upshifted relative to those of their Os counterparts. Stated differently, the Re corrole dimers are dramatically easier to reduce, reflecting electron addition to δ* versus π* molecular orbitals for Re and Os corrole dimers, respectively. The data also imply electrochemical HOMO-LUMO gaps of only 1.0–1.1 V for rhenium corrole dimers, compared with values of 1.85–1.90 V for their Os counterparts. These HOMO–LUMO gaps rank among the first such values reported for quadruple-bonded transition-metal dimers for any type of supporting ligand, porphyrin-type or not.