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The reactions of newly designed lithiated triamidoamines Li3LR (R = iPr, Pen, and Cy2) with VCl3(THF)3 under N2 yielded dinitrogen-divanadium complexes with a μ-N2 between vanadium atoms [V(LR)2(μ-N2)] (R = iPr (1) and Pen (2)) for the former two, while not dinitrogen-divanadium complexes but a mononuclear vanadium complex with a vacant site, [V(LCy2)] (R = Cy2 (3)), were obtained for the third ligand. The V-NN2 and N-N distances were 1.7655(18) and 1.219(4) Å for 1 and 1.7935(14) and 1.226(3) Å for 2, respectively. The ν(14N-14N) stretch
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