Nitrogen-containing organic compounds are valuable in many fields of science and industry. The most reliable method for the construction of C(sp(2) )-N bonds is undoubtedly palladium-catalyzed amination. In spite of the great achievements made in this area, the use of expensive Pd-based catalysts constitutes an important limitation for large-scale applications. Since nickel is the least expensive and most abundant among the group 10 metals, the interest in Ni-based catalysts for processes typically catalyzed by palladium has grown considerably over the last few years. Herein, we revise the development of Ni-catalyzed amination reactions, emphasizing the most relevant and recent advances in the field.

The experimental and computational characterization of a series of dialkylterphenyl phosphines, PR2Ar′ is described. The new P‐donors comprise five compounds of general formula PR2ArDtbp2 (R=Me, Et, iPr, c‐C5H9 and c‐C6H11); ArDtbp2 = 2,6‐C6H3‐(3,5‐C6H3‐(CMe3)2)2), and another five PR2Ar′ phosphines containing the bulky alkyl groups iPr, c‐C5H9 or c‐C6H11, in combination with Ar′=ArXyl2 , ArXyl'2 , or ArPh2 (L1–L10). Steric and electronic parameters have been determined computationally and from IR and X‐ray data obtained for the phosphines and for some derivatives, including tricarbonyl and dicarbonyl nickel complexes, Ni(CO)3(PR2Ar′) and Ni(CO)2(PR2Ar′). In the solid state, the free phosphines PR2Ar′ adopt one of the three possible structures formally related by rotation around the Cipso−P bond. Details on their relative energies and on the influence of the free phosphine structure on its coordination chemistry towards Ni(CO)n (n = 2, 3) fragments has been obtained by experimental and computational methods.

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Ni‐catalyzed C−S cross‐coupling reactions have received less attention compared with other C‐heteroatom couplings. Most reported examples comprise the thioetherification of most reactive aryl iodides with aromatic thiols. The use of C−O electrophiles in this context is almost uncharted. Here, we describe that preformed Ni(II) precatalysts of the type NiCl(allyl)(PMe2Ar’) (Ar’=terphenyl group) efficiently couple a wide range of (hetero)aryl halides, including challenging aryl chlorides, with a variety of aromatic and aliphatic thiols. Aryl and alkenyl tosylates are also well tolerated, demonstrating, for the first time, to be competent electrophilic partners in Ni‐catalyzed C−S bond formation. The chemoselective functionalization of the C−I bond in the presence of a C−Cl bond allows for designing site‐selective tandem C−S/C−N couplings. The formation of the two C‐heteroatom bonds takes place in a single operation and represents a rare example of dual electrophile/nucleophile chemoselective process.

Bulky terphenyl phosphane ligands PMe2Ar’ (Ar’ = terphenyl group) facilitate the isolation of zero-valent bis-phosphane complexes of nickel, palladium and platinum. The former show coordination numbers greater than two in...