I : A suspension of 1 g of TiCI, in 15 mL of dry CH,CN was heated under reflux in an inert atmosphere (Ar) until a deep-blue solution was obtained. This was then treated dropwise with a solution of 1.2 g of N,N',N"-trimethyl-l,4,7-triazacyclononane (L) in 10 mL of CH,CN. After 30 minutes' stirring at 20 C a turquoise colored precipitate of LTiCI, was recovered by filtration (yield: 92%). UV/VIS (CH,CN): I,,, = 690 nm (c = 30); per, (293 K) = 1.7 pH 20 mL of a methanolic solution of 0.5 g of LTiCI, and 1 g of sodium benzoate was heated under reflux in an inert atmosphere (Ar) for 30 min. The resulting black-violet solution was treated with 1 g of NaPF,. After 12 h at S'C, blackviolet crystals of 1 were formed in 80% yield. IR (KBr): i. = 1541 [;.~(C-~O)].
1397 [v5(C-O)], 685 cm-' [vJ&O-Ti)];
UV!VIS (CH,CN): i . , , , = 450 ( F = 2100). 595 (sh) nm.-2: a solution of 0.8 g of L in 20 mL of dimethylformarnide which contained about 1 O h H,O was purged with argon and treated with 0.51: of TiCI,. The resulting suspension was heated under reflux for 30 min. After cooling to 5 'C a bright blue, microcrystalline precipitate of 2 was recovered by filtration (yield 45%). IR(KBr): i. = 745cm-' [r, (Ti 0-Ti)]; UVjVIS (CH,CN): I,,, = 570 nm (c = 520 mol-' cm-'), 750 nm (sh). Magnetic moment: p = 1.7 pB per Ti atom (90-298 K). All the complexes gave correct elemental analyses (C,H,N,CI).