Reactions of Cp_2M (M = Ni, V) with dilithium diamido-aryl reagents; Retention and oxidation of the transition metal ions

摘要

The reactions of dilithium 1,2-diamidobenzene, [1,2-(HN)_2C_6H_4]Li_2 (L~1H_2)Li_2, and dilithium 1,8-diamidonaphthalene, [1,8-(NH)_2C_(10)H_6]Li_2 (L~2H_2)Li_2, with Cp_2Ni and Cp_2V have been used to obtain the new complexes (L~2H_2)_2Ni{Li(THF)_2}_2 (3), (L~2H_2)_3V{Li(THF)_2}_3 (4) and (L~1H_2)_6Ni_6·{[(L~1H_2)_3(L~1H)_3Ni_6Li(THF)]~(2-)·2[Li(THF)_4]~+} (5), in which retention or oxidation of the initial metal(ii) centre is observed. Whereas 3 and 4 contain one transition metal ion within ion-paired structures, 5 has a complicated co-crystalline composition which contains octahedral Ni_6-cages constructed from six square-planar (16e) Ni~(II) centres.