Using titanocene synthon [Cp2Ti(Me3SiC2SiMe3)] the selective conversion of aryl-substituted triphosphiranes P3Ar3 into Cp2TiP2Ar2 complexes was achieved.

New N‐heterocyclic olefins (NHOs) are described with functionalization on the ligand heterocyclic backbone and terminal alkylidene positions. Various PdII–NHO complexes have been formed and their use as pre‐catalysts in Buchwald–Hartwig aminations was explored. The most active system for catalytic C−N bond formation between hindered arylamine and arylhalide substrates was accessed by combining a backbone methylated NHO with [Pd(cinnamyl)Cl]2 in the presence of NaOtBu as a base. In these active systems evidence suggests that catalysis is mediated by colloidal palladium metal, highlighting a different coordination ability of NHOs in comparison with commonly used N‐heterocyclic carbene co‐ligands.

Cyclotriarsanes are rare and described herein is a scalable synthetic protocol towards aryl-substituted derivatives. Their reactivity towards [Cp2Ti(C2(SiMe3)2)], affording titanocene diarsene complexes, and N-heterocyclic carbenes (NHCs) is discussed.

Terphenyl(bisamino)phosphines have been identified as effective ligands in cationic gold(I) complexes for the hydroamination of acetylenes. These systems are related to Buchwald phosphines and their steric properties have been evaluated....