The high-temperature (∼180 °C) reaction between free-base meso-triarylcorroles and Re2(CO)10, followed by exposure to PCl3 and thiols (or elemental sulfur), affords rhenium-sulfido (ReS) corroles in 67–76% yields. The use of shorter reaction times, lower temperatures (∼130 °C), and a dithiol (e.g., ethane-1,2-dithiol) also allows the isolation of rhenium-dithiolato corroles, presumptive intermediates on the path to ReS corroles. The ReS corroles exhibit high thermal stability and two reversible oxidations and reductions in their cyclic voltammograms, with redox potentials nearly identical to those observed for analogous ReO corroles. The electrochemical HOMO–LUMO gaps of the complexes, at 2.2 eV, are consistent with ligand-centered oxidation and reduction. The UV–vis spectra of ReS corroles, on the other hand, differ significantly from those of their ReO counterparts. Scalar-relativistic DFT calculations suggest that this difference reflects low-energy LUMO+2 and LUMO+3 levels, consisting of Re–S π-antibonding interactions; the ReO corroles, in contrast, exhibit a larger LUMO+1/LUMO+2 gap, as expected for a relatively classical Gouterman-type metalloporphyrin analogue. The high stability of ReS corroles is consistent with geochemists’ view of rhenium as a moderately chalcophilic element (i.e., one that partitions into sulfide melts) as well as with a recent quantitative analysis of thiophilicity, which indicates that rhenium’s oxophilicity and thiophilicity are essentially evenly balanced.

Square-planar bis­[1,2-bis­(3,5-di­methyl­phen­yl)ethyl­ene-1,2-di­thiol­ato(1–)]nickel(II) crystallizes on an inversion center in monoclinic P21/c in a packing arrangement defined by a dense network of inter­molecular methyl C—H→πarene hydrogen bonds.

The title compound crystallizes as closely associated pairs across an inversion center, with near approach enabled by Ni⋯S inter­molecular contacts of 3.396 (2) Å and bending of the di­thiol­ene ligands away from one another.