The multigram syntheses of the protio ligands (2-NC5H4)CH2N(CH2CH2NHSiMe2R)2 (R=Me,H2N2NN'3;R=tBu,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(CH2-CH2NHTs)2 (2). Reaction of H2N2NN'or H2N2NN* with nBuLi 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(CH2CH2-NHTs)2