Exploring Mechanisms in Ni Terpyridine Catalyzed C–C Cross-Coupling Reactions—A Review

Abstract

Abstract:In recent years, nickel has entered the stage for catalyzed C-C cross-coupling reactions, replacing expensive palladium, and in some cases enabling the use of new substrate classes. Polypyridine ligands have played an important role in this development, and the prototypical tridentate 2,2 :6 ,2 -terpyridine (tpy) stands as an excellent example of these ligands. This review summarizes research that has been devoted to exploring the mechanistic details in catalyzed C-C cross-coupling reactions using tpy-based nickel systems.

Ddpd as Expanded Terpyridine: Dramatic Effects of Symmetry and Electronic Properties in First Row Transition Metal Complexes

“…Pincer-type [1,2] terpyridine ligands (2,2 :6 ,2 -terpyridine tpy; pincer ligands are tridentate, 6-electron donor ligands that enforce a meridional coordination geometry on the metal centre) and their manifold complexes [3] play a central role in key fields of coordination chemistry with important applications in supramolecular chemistry [4][5][6][7][8][9][10][11][12][13][14], spin-crossover (SCO) phenomena [15][16][17][18], homogeneous catalysis [19][20][21], biomedical applications [22], redox non-innocence [23][24][25][26][27] or photochemistry [6,7,28], to name just a few.…”

Metal‐Terpyridine Complexes in Catalytic Application – A Spotlight on the Last Decade

“…Thereby, the electron‐density at the metal is reduced and stabilization by appropriate ligands, such as phosphines or polypyridyl systems, is required. In this context, terpyridines have been identified as versatile chelating ligands . Ciszeswki et al .…”

“…Thereby, the catalytically active species was generated in situ by electrochemical one‐electron reduction of [(tpy)NiBr 2 ]. The details of the reaction mechanism have been studied intensively and are summarized elsewhere . In brief, the re‐oxidation by a perfluoroalkyl halide gave perfluoroalkyl radicals which, in turn, added to α‐methyl styrene.…”

Metal-supported and -assisted stereoselective cooperative photoredox catalysis

“…Nickel(II) complexes have received great attention due to their success in catalytic processes, especially with regard to replacing the expensive palladium in C-C cross-coupling reactions and in reductive coupling. [55][56][57] Nickel behaves very differently from palladium. Thus, consistent deviations in the mechanisms of catalysed reactions are present, as for example radical pathways are more favoured.…”