The Z-alkene geometry is prevalent in various chemical compounds, including numerous building blocks, fine chemicals, and natural products. Unfortunately, established Mo, W, and Ru Z-selective catalysts lose their selectivity at high temperatures required for industrial processes like reactive distillation, which limits their synthetic applications. To address this issue, we develop a catalyst capable of providing Z-alkenes with high selectivity under harsh conditions. Our research reveals a dithiolate ligand that, stabilised by resonance, delivers high selectivity at temperatures up to 150 °C in concentrated mixtures. This distinguishes the dithioquinoxaline complex from existing Z-selective catalysts. Notably, this trait does not compromise the new catalyst’s usability under classical conditions, matching the activity of known stereoretentive catalysts. Density Functional Theory calculations were employed to understand the reaction mechanism and selectivity, and to investigate the poisoning that the catalyst may undergo and how it competes with catalytic activity. Furthermore, the quinoxaline-based catalyst enables the valorisation of bio-sourced alkene feedstocks and the production of agricultural sex pheromones for pest control.

We report a new high-yield synthesis of so far not accessible tetraphenylphosphonium methylcarbonate Ph₄P[OCO₂Me] via solvothermal fluoride-induced demethylation and MeF elimination at Me₂CO₃ (DMC) by Ph₄P–F, structurally characterized as λ⁵-fluorophosphoran by XRD. The synthetic value of Ph₄P[OCO₂Me] key compound for preparing nearly all kinds of other Ph₄P[anion] salts with perfectly crystallizing (not symmetry frustrated) cation is demonstrated by examples beyond ionic liquid research: a complete set of silylchalcogenide salts Ph₄P[ESiMe₃] (E = S, Se, and Te) including the first example of a structurally characterized non-coordinating, naked [Te–SiMe₃]⁻ anion is presented. With this set of soft Lewis bases and metal organic Lewis acids [Cp₃La] at hand, a comprehensive series of crystalline 1 : 1 lanthanate complexes Ph₄P[Cp₃La–ESiMe₃] has been prepared. Their structural features and trends such as complexation induced Si–E bond elongation and a pronounced trend in La–E–Si bond angle contraction with E = S < Se < Te are discussed. Heteronuclear ¹H, ¹³C, ²⁹Si, and ¹³⁹La NMR studies provide a set of ¹³⁹La NMR shifts for homologs of heavy chalcogen–lanthanum complexes.

Metal-containing heteraadamantanes are compounds of interest due to their spectroscopic and magnetic properties, which make them promising materials for non-linear optics and semiconductors. Herein we report the comprehensive structural characterization of a new coordination compound of the formula [(µ-OH′)₂(µ-OH″)₄(O = P(Ph₂)CH₂CH₂(Ph₂)P = O)₄{Fe(t-BuOH)}₄](PF₆)₄(Cl)₂ with the chelating ligand Ph₂P(O)-CH₂CH₂-P(O)Ph₂. The compound crystallizes as a polynuclear metal complex with the adamantane-like core [Fe₄O₆] in the space group I-43d of a cubic system. The single-crystal XRD analysis showed that the crystal contains one symmetrically independent octahedrally coordinated Fe atom in the oxidation state +3. The adamantine-like scaffold of the Fe complex is formed by hydroxy bridging oxygen atoms only. Hirshfeld surface analysis of the bridging oxygen atoms revealed two types of µ-OH groups, which differ in the degree of exposure and participation in long-range interactions. Additionally, the Hirshfeld surface analysis supported by the enrichment ratio calculations demonstrated the high propensity of the title complex to form C-H^…Cl, C-H^…F and C-H^…O interactions.