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A cyclic tri-nuclear α-diimine nickel(0) complex [{Ni(μ-LMe-2,4)}3] (2) was synthesized from a "pre-organized", trimerized trigonal LNiBr2-type precursor [Ni3(μ2-Br)3(μ3-Br)2(LMe-2,4)3]·Br (1; LMe-2,4 = [(2,4-Me2C6H3)NC(Me)]2). In complex 2, the α-diimine ligands not only exhibit the normal N,N'-chelating mode, but they also act as bridges between the Ni atoms through an unusual π-coordination of a C[double bond, length as m-dash]N bond to Ni. Complex 2 is able to catalyze the cyclotrimerization of alkynes to form substituted benzenes in good yield and regio-selectivity for the 1,3,5-isomers, which is found to vary with the nature of the alkyne employed. This complex represents a convenient self-supported nickel(0) catalyst with no need for additional ligands and reducing agent.

Cyclotrimerization of alkynes catalyzed by a self-supported cyclic tri-nuclear nickel(0) complex with α-diimine ligands