The meta-terphenyl diphosphine, m-P2: 1, was utilized to support Ni centers in the oxidation states 0, I and II. A series of complexes bearing different substituents and/or ligands at Ni were prepared to investigate the dependence of metal-arene interactions on oxidation state and substitution at the metal. Compound (m-P2)Ni (2), shows close Ni(0)-arene interactions between the metal centre and the central arene ring of the terphenyl ligand both in solution and the solid-state. These interactions are significantly less pronounced in Ni(0) complexes bearing L-type ligands (2-L: L = CH3CN, CO, Ph2CN2), Ni(I)X complexes [3-X: X = Cl, BF4, N3, N3B(C6F5)3] and (m-P2)Ni(II)Cl2 (4). Complex 2 reacts with substrates such as diphenyldiazoalkane, sulfur ylides (Ph2S=CH2), organoazides (RN3: R = para-C6H5OMe, para-C6H5CF3, 1-adamantyl) and N2O with the locus of observed reactivity dependent on the nature of the substrate, leading to isolation of an η1-diphenyldiazoalkane adduct (2-Ph2CN2), methylidene insertion into a Ni-P bond, followed by rearrangement of a nickel-bound phosphorus ylide (5) to a benzylphosphine (6), Staudinger oxidation of the phosphine arms and metal-mediated nitrene insertion into an arene C-H bond of 1 to give the insertion product 8, all derived from the same compound (2). Hydrogen atom abstraction from a nickel(I)-amide (9) and resulting nitrene transfer chemistry supports the viability of nickel-imide intermediates in the reaction of 1 with 1-azido-arenes.

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