Tungsten Biscorroles: New Chiral Sandwich Compounds.

The oxidative metalation method, involving the interaction of free-base meso-triarylcorroles and W(CO)6 in refluxing decalin, led to a set of three tungsten(VI) biscorroles, the first homoleptic sandwich compounds involving corroles. Single-crystal X-ray structures of two of the complexes revealed square-antiprismatic coordination and strongly domed corroles with long W-N distances of 2.15-2.22 Å and a substantial displacement of ∼1.17 Å of the metal relative to the mean N4 planes of the ligands. The structures correspond to approximate C2 symmetry and are thus chiral. DFT calculations strongly indicate that the enantiomers are configurationally stable and hence amenable to chiral resolution. Their other notable properties include a strongly blueshifted Soret band at (357±2) nm, a relatively intense π→W(dz2 ) near-IR feature at (781±3) nm, and a low electrochemical HOMO-LUMO gap of approximately 1.3 V. The results obtained herein suggest that metallobiscorroles may emerge as a new class of inherently chiral chromophores with novel optical and electrochemical properties.