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 influence of a 2-pyridinyl substituent on the catalytic performance of aryliodide as a catalyst in iodine(III) chemistry was explored. An efficient Lews-base adduct between the pyridine nitrogen and the electrophilic iodine(III) center was identified and confirmed by X-ray analysis. This arrangement was shown to generate a kinetically competent superior catalyst structure for the catalytic dioxygenation of alkenes. It introduces the concept of Lewis-base adduct formation as a kinetic factor in iodine(I/III) catalysis.

The platinum complex [Pt(I(t)Bu')(I(t)Bu)][BAr(F)] is a very efficient catalyst in the synthesis of diaminoboranes through dehydrocoupling of amine-boranes and amines. Shimoi-type, η(1)-BH complexes are key intermediates in the 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...