Inorganic Chemistry, Vol.47, No.15, 6692-6700, 2008
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-Pr-i(2)-C6H3; R = H, SiMe3)
Addition reaction of ArN(SiMe3)M (Ar = Ph or 2,6-Pr-i(2)-C6H3 (Dipp); M = Li or Na) to 2 equivalents of alpha-hydrogen-free nitrile RCN (R = dimethylamido) gave the dimeric [M{N(Ar)C(NMe2)NC(NMe2)N(SiMe3)}](2) (11 a, Ar = Ph, M = Li; 1b, Ar = Ph, M = Na; 1c, Ar = Dipp, M = Li). Id was obtained by hydrolysis of 1c at ambient temperature. Treatment of a double ratio of 1 a 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 center dot 6H(2)O 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 H-1, C-13 NMR, 1c by Li-7, and 6 by P-31 NMR as well. The structural features of these complexes were described in detail.