Nickel, which is able to access multiple oxidation states, offers versatile reactivity patterns while being earth-abundant and more affordable than other noble-metal catalysts such as palladium or rhodium. As a result, the usage of nickel in organic synthesis has received considerable attention in recent years and this has led to the development of numerous useful transformations. On the other hand, the study of stoichiometric organometallic nickel chemistry has been overshadowed by the advances in catalysis. Given the mentioned benefits of nickel, stoichiometric organometallic nickel chemistry holds great promise for the discovery of novel reactivities, overriding limitations of catalytic strategies as well as the study of mechanisms.

This doctoral thesis presents the synthesis of organometallic nickel complexes and their use as versatile exploratory platforms. In the first part, a general protocol for the preparation of nickel(II) oxidative addition complexes derived from drug-like molecules and their potential for late-stage C(sp²)–C(sp³) diversification is depicted. In the second part, the synthesis of dinuclear nickel(I) oxidative addition complexes of aryl pivalates and their capability to undergo s Ni–C(sp²) bond migration is described. Finally, the synthesis of Ni(I)– and Ni(II)–alkyl complexes containing b-hydrogen atoms is presented as tools to uncover fundamental mechanistic insights of Ni-catalysed chain-walking reactions.

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