A straightforward synthesis of cyclopropenylidene-stabilized phosphenium cations 1 a–g through the reaction of [(iPr₂N)₂C₃⁺Cl]BF₄ with secondary phosphines is described. Their donor ability was evaluated by analysis of the CO stretching frequency in Rh complexes [RhCl(CO)L₂](BF₄)₂ and electrochemical methods. The cyclopropenium ring induces a phosphite-type behavior that can be tuned by the other two substituents attached to the phosphorus atom. Despite of the positive charge that they bear, phosphenium cations 1 a–g still act as two-electron donor ligands, forming adducts with Pd^II and Pt^II precursors. Conversely, in the presence of Pd⁰ species, an oxidative insertion of the Pd atom into the C_carbene–phosphorus bond takes place, providing dimeric structures in which each Pd atom is bonded to a cyclopropenyl carbene while two dialkyl/diaryl phosphide ligands serve as bridges between the two Pd centers. The catalytic performance of the resulting library of Pt^II complexes was tested; all of the cationic phosphines accelerated the prototype 6-endo-dig cyclization of 2-ethynyl-1,1′-biphenyl to afford pentahelicene. The best ligand 1 g was used in the synthesis of two natural products, chrysotoxene and epimedoicarisoside A

A series of novel 3- and 5-biaryl-substituted isoxazoles was prepared by a rapid microwave-assisted four-component three-step synthesis: concatenating Sonogashira coupling, cyclocondensation, and Suzuki coupling in a one-pot fashion. The Pd-catalyst was successfully employed in the sense of a sequentially catalyzed process, i.e., without the addition of further catalyst loading. Biaryl-substituted isoxazoles with donor–acceptor decoration possess remarkable photophysical properties, such as high fluorescence quantum yields in solution up to ΦF = 0.86 and large Stokes shifts up to 10,000 cm−1. The experimental absorption and emission characteristics can be reproduced and rationalized by computations on the DFT (density functional theory) and TDDFT (time-dependent density functional theory) level of theory.