Synthesis and Structures of Selected Triazapentadienate of Li, Mn, Fe, Co, Ni, Cu(I), and Cu(II) using 2,4-N,N′-Disubstituted 1,3,5-Triazapentadienate Anions as Ancillary Ligands: [N(Ar)C(NMe₂)NC(NMe₂)N(R)]⁻ (Ar = Ph, 2,6-ⁱPr₂−C₆H₃; R = H, SiMe₃)

Addition reaction of ArN(SiMe3)M (Ar = Ph or 2,6-iPr2−C6H3 (Dipp); M = Li or Na) to 2 equivalents of α-hydrogen-free nitrile RCN (R = dimethylamido) gave the dimeric [M{N(Ar)C(NMe2)NC(NMe2)N(SiMe3)}]2 (1a, Ar = Ph, M = Li; 1b, Ar = Ph, M = Na; 1c, Ar = Dipp, M = Li). 1d was obtained by hydrolysis of 1c at ambient temperature. Treatment of a double ratio of 1a or 1b with anhydrous MCl2 (M = Mn, Fe, Co) yielded the 1,3,5-triazapentadienato complexes [M{N(Ph)C(NMe2)NC(NMe2)N(SiMe3)}2] (M = Mn, 2; Fe, 3; Co, 4) and with NiCl2·6H2O gave [M{N(Ph)C(NMe2)NC(NMe2)N(H)}2] (M = Ni, 5). Treatment of an equiv of 1c with anhydrous CuCl in situ and in air led to complexes [{N(Dipp)C(NMe2)NC(NMe2)N(SiMe3)}CuPPh3] 6 and [Cu{N(Dipp)C(NMe2)NC(NMe2)N(H)}2] 7, respectively. 1c, 1d, and 2−7 were characterized by X-ray crystallography and microanalysis. 1c, 1d, 5, and 6 were well characterized by 1H, 13C NMR, 1c by 7Li, and 6 by 31P NMR as well. The structural features of these complexes were described in detail.