Redox-Active Ligands and Organic Radical Chemistry

Knowledge about bonding in diiminepyridine (L) halide, alkyl, and dinitrogen complexes of the metals iron, cobalt, and nickel is summarized, and two new examples are added to the set: L1Ni(Me) and L1Ni(N2). Reactivity of these types of complexes is discussed in terms of organic radical chemistry. New C−C couplings with L2CoAr complexes are described and proposed to involve halide abstraction and radical coupling. Calculations support the high tendency of the diiminepyridine ligand to accept an electron coming from a metal−carbon bond and so facilitate loss of a radical.