The synthesis of the following crystalline complexes is described: [Li(L)(thf)2] (2), [Li(L)(tmeda)] (3), [MCl2(L)] [M = Al (4), Ga (5)], [In(Cl)(L)(µ-Cl)2Li(OEt2)2] (6), [In(Cl)(L){N(H)C6H3Pri2-2,6}] (7), [In(L){N(H)C6H3Pri2-2,6}2] (8), [{In(Cl)(L)(µ-OH)}2] (10), [L(Cl)In–In(Cl)(L)] (11) (the thf-solvate 11a, the solvate-free 11b and the hexane-solvate 11c), [{In(Cl)L}2(µ-S)] (12) and [InCl2(L)(tmeda)] (13) ([L]− = [{N(C6H3Pri2-2,6)C(H)}2CPh]−). From H(L) (1), via Li(L) in Et2O, and thf, tmeda, AlCl3, GaCl3 or InCl3 there was obtained 2, 3, 4, 5 or 6, respectively in excellent yield. Compound 6 was the precursor for each of 7–11, 13 and [{InCl3(tmeda)2{µ-(OSnMe2)2}}] (14) by treatment with one (7) or two (8) equivalents of K[N(H)(C6H3Pri2-2,6)], successively Li[N(SiMe3)(C6H3Pri2-2,6)] and moist air (10), Na in thf (11a), tmeda (13), or successively tmeda and Me3SnSnMe3 (14). Crystals of 11b (with an equivalent of In) and 11c were obtained from InCl or thermolysis of [In(Cl)(L){N(SiMe3)(C6H3Pri2-2,6)}] (9) {prepared in situ from 6 and Li[N(SiMe3)(C6H3Pri2-2,6)] in Et2O}, respectively. Compound 12 was obtained from a thf solution of 11a and sulfur. X-Ray data for crystalline 1–6, 8, 11a, 11b, 11c, 12 and 14 are presented. The M(L) moiety in each (not the L-free 14) has the monoanionic L ligated to the metal in the N,N′-chelating mode. The MN1C1C2C3N2 six-membered M(L) ring is π-delocalised and has the half-chair (2, 3 and 11) or boat (4–8, 10 and 13) conformation.