An unprecedentedly thermo‐ and air‐stable Pd0 complex from readily available electron‐poor trifluoromethylated phosphine was serendipitously discovered. As detailed and comparative DFT calculations indicate, the stability of the complex is associated with unusually strong ligand–ligand noncovalent interactions. The unique stability and the presence of hydrophobic structural elements of the complex offer several practical advantages, which were exploited in catalytic Suzuki–Miyaura coupling reactions.

The exploration of the direct arylation capacity of a unique, thermally stable, and air‐stable Pd0–phosphine catalyst is reported. Besides decisively contributing to catalyst robustness, the electron‐deficient trifluoromethyl‐substituted triphenylphosphine ligands make the palladium center more electron‐deficient and accelerate the direct arylation step. The combination of only 0.5–2 mol‐% of the catalyst and a substoichiometric quantity of pivalic acid generates an efficient system to promote biaryl‐forming reactions of a broad range of electronically varied hetarenes and aryl bromides. The observed regioselective arylations suggest that a concerted metalation–deprotonation pathway is involved in the C–H activation step.

Superstable Palladium(0) Complex as an Air-and Thermostable Catalyst for Suzuki Coupling Reactions. -A novel tris(triphenylphosphine) Pd-complex with unprecedented temperature and air-stability is discovered and successfully used as catalyst for Suzuki coupling reactions of aryl bromides with aryl dioxaborolanes. -(JAKAB, A.; DALICSEK, Z.; HOLCZBAUER, T.; HAMZA, A.; PAPAI*, I.; FINTA, Z.; TIMARI, G.; SOOS, T.; Eur. J. Org. Chem. 2015, 1, 60-66, http://dx.