The Z-alkene geometry is ubiquitous in a wide range of building blocks, fine chemicals, and natural products. Because well-established Mo, W, and Ru Z-selective catalysts were found to lose their selectivity at higher temperatures required for industrially interesting reactive distillation mRCM, we opted for the development of a catalyst capable of providing Z-alkenes in high selectivity, also under more harsh conditions. It was found that the new type of stabilised by resonance dithiolate ligand can provide high selectivity at temperatures up to 150 °C in highly concentrated reaction mixtures. Computational studies were employed to assess the observed enhancements conferred by these novel ligands, operating under the assumption that the primary limitation to achieving Z selectivity lies in the propensity for 1,2-sulphide displacement. While no discernible thermodynamic enhancements were identified along the Z-product route, there is evidence suggesting a reduction in the kinetics of the deactivation pathway with the newly proposed ligand, particularly when considering proper speciation. Furthermore, the concurrent characterization via parallel DFT supports the notion of a nucleophilic decrease in the sulphur nuclei within the 2,3-dithioquinoxaline ligand structure.