Developing Ni and Pd precatalysts for demanding cross-coupling reactions

This chapter summarizes our efforts to build efficient catalytic protocols based on Ni and Pd for cross-coupling reactions, in particular those involving demanding substrates. First, we describe the application of Ni(II)-allyl and Ni(0)-olefin complexes supported by N-heterocyclic carbenes (NHCs) as precatalysts for C-C and C-heteroatom bond formation. In the following section, we introduce a family of bulky, electron-rich ligands, the dialkylterphenyl phosphanes, and discuss their coordination and stereoelectronic properties, emphasizing their aptitude to stabilize low-coordinate structures. Finally, in the last section, we discuss the use of terphenyl phosphanes as ancillary ligands in Ni- and Pd-catalyzed reactions involving C-O electrophiles. In addition, we provide detailed mechanistic information, supported by experimental and computational data, for some of the reactions studied.