Formation of exceptional monomeric YPhos–PdCl2 complexes with high activities in coupling reactions

Abstract

The use of well-defined palladium(II) complexes as precatalysts for C–X cross-coupling reactions has improved the use of palladium catalysts in organic synthesis including large-scale processes. Whereas sophisticated Pd(II) precursors have been developed in the past years to facilitate catalyst activation as well as the handling of systems with more advanced monophosphine ligands, we herein report that simple PdCl₂ complexes function as efficient precatalysts for ylide-substituted phosphines (YPhos). These complexes are readily synthesized from PdCl₂ sources and form unprecedented monomeric PdCl₂ complexes without the need for any additional coligand. Instead, these structures are stabilized through a unique bonding motif, in which the YPhos ligands bind to the metal through the adjacent phosphine and ylidic carbon site. DFT calculations showed that these bonds are both dative interactions with the stronger interaction originating from the electron-rich phosphine donor. This bonding mode leads to a remarkable stability even towards air and moisture. Nonetheless, the complexes readily form monoligated LPd(0) complexes and thus the active palladium(0) species in coupling reactions. Accordingly, the YPhos–PdCl₂ complexes serve as highly efficient precatalysts for a series of C–C and C–X coupling reactions. Despite their simplicity they can compete with the efficiency of more complex and less stable precatalysts.