The multigram syntheses of the protio ligands (2-NC5H4)CH2N(CH2CH2NHSiMe2R)(2) (R = Me, H2N2NN' 3; R = Bu, H2N2NN' 4) are described via reactions of the previously reported (2-NC5H4)CH2N(CH2CH2NH2)(2) (1). A new synthesis of 1 is reported starting from 2-aminomethylpyridine and N-tosylaziridine, proceeding via (2-NC5H4)CH2N(CH2CH2NHTs)(2) (2). Reaction of H2N2NN' or H2N2NN' with (BuLi)-Bu-n gives good yields of the dilithiated derivatives Li2N2-NN' and Li2N2NN'. Reaction of H2N2NN' or H2N2NN' with [MCl2(CH2SiMe3)(2)(Et2O)(2)] gives the cis-dichloride complexes [MCl2(L)] (L = N2NN', M = Zr 7 or Hf 8; L = N2NN', M = Zr 9). The corresponding reactions of H2N2NN' or H2N2NN' with [Zr(NMe2)(4)] afford the bis(dimethylamide) derivatives [Zr(NMe2)(2)(L)] (L = N2NN' 10 or N2NN' 11). All of these protonolysis reactions proceed smoothly and in good yields. Attempts to prepare the titanium complexes [Ti(X)(2)(N2NN')] (X = Cl or NMe2) were unsuccessful, The X-ray crystal structures of (2-NC5H4)CH2N(CH2CH2NHTs)(2).EtOH, [ZrCl2(N2NN')].0.5C(6)H(6), [Zr(NMe2)(2)(N2NN')], and [Zr(NMe2)(2)(N2NN')] are reported.