Decoration with N-heterocyclic olefins (NHOs) turns 2,2′-bipyridine into an electron-rich, proton-switchable ligand. The switching range is remotely tunable by the NHO backbone and can surpass the do...

Phosphonioacetylides are rod-shaped, neutral carbon donors with ambiphilic character at the terminal carbon. Despite their analogy to CO and isocyanides, they remain underexplored due to their high reactivity, and only one isolable free phosphonioacetylide has been reported. Here, we describe two new isolable, room-temperature-persistent examples stabilized either by two N-heterocyclic imines (NHIs) bearing bulky, flexible tert-octyl groups or by a single dipp-substituted NHI combined with alkyl substituents. Comprehensive characterization (SCXRD, NMR, IR, MS, DFT) confirms their strong donor properties and the accessibility of the reactive C2 unit. DFT analysis quantify how the substituents at phosphorus modulate the frontier molecular orbital energies, spanning a wide range of σ and π-donor strengths and π-acceptor abilities, with trends that mirror those of the corresponding phosphines. Both phosphonioacetylides readily form AuI complexes, whereas the less electron-rich compound shows the tendency to eliminate its C2 moiety thermally or upon hydrolysis. These results establish design principles for stabilizing and tuning phosphonioacetylides and open avenues for their use in coordination chemistry and catalysis.

Das Frauenförderungsprogramm „UIBK-FemCareer-Fellowship“ der Universität Innsbruck unterstützt internationale Jungwissenschaftlerinnen zu Beginn ihrer akademischen Laufbahn. Ziel ist es, den Wissensch...

Schwefelhexafluorid ist ein extrem starkes und langlebiges Treibhausgas. Ein Team um Fabian Dielmann von der Universität Innsbruck präsentiert nun ein einfaches Verfahren zur Zersetzung des industriel...

SF₆ is a potent greenhouse gas, and its current degradation needs harsh conditions and post-treatment. Herein one-step mineralisation at room temp using KOH in water/IPA under UV is shown via acetone-...

The synthesis and reactivity of secondary phosphines carrying two N-heterocyclic imine substituents are reported. These highly electron-rich phosphines feature a polarized P–H bond, with computational...

Rod-shaped neutral carbon ligands such as carbon monoxide and isocyanides play a central role in organometallic chemistry but are relatively weak electron donors compared to N-heterocyclic carbenes. P...

Although fullerene derivatization has been extensively studied for decades, zwitterionic adducts with neutral Lewis bases are rare, and those with tertiary phosphines remain elusive. This work present...