Formation and homolytic cleavage of the Ni(II)–styryl σ‐bond

Abstract A Ni–carbon σ‐bond is formed from biscyclooctadienenickel(0) and styrene in the presence of organic acids. Homolytic cleavage of this bond gives free radicals. The mechanism of formation and disappearance of the radical‐supplying species is deduced from kinetic and other data. A competing coordinated ligand insertion reaction is discussed.