Titanium(IV) and Zirconium(IV) Amido Complexes Derived from the Azaoxa Macrocycle 3,3-Dimethyl-1,5-diaza-8-oxacyclodecane

The novel tridentate azaoxa macrocycle [O(NH)2], 3,3-dimethyl-1,5-diaza-8-oxacyclodecane, can be singly or doubly
lithiated with nBuLi at the secondary amine N atoms, giving [O(NH)N]Li and [O(N)2]Li2, respectively, and further
elaborated with introduction of TMS substituents via reaction with (TMS)Cl. Aminolysis of [Ti(NMe2)2Cl2] or
[Zr(NR2)2Cl2(THF)2] with [O(NH)2] in toluene gave the distorted octahedral M[O(NH)N](NR2)Cl2 (M = Ti, R = Me;
M = Zr, R = Me or Et), in which the macrocycle functions as a monoanionic ligand via an amido, an amine, and
an ether functionality. Salt metathesis of [Zr(NEt2)2Cl2(THF)2] with [O(NH)N]Li in toluene afforded Zr[(O(NH)N)](NEt2)2Cl, the structure of which also confirms tridentate macrocycle coordination via one amido, one amine, and
one ether group; in contrast, analogous salt metathesis involving [Zr(NEt2)2Cl2(THF)2] and [O(N)2Li2] gave the
“sandwich” complex [(ON2)2Zr], with the macrocycle behaving as a dianionic ligand (Porter, R. M.; et al. Dalton
Trans. 2005, 427). Finally, treatment of [O(NH)2] with AlMe3 gave the simple donor−acceptor adduct [O(NH)2]AlMe3, which resisted alkanolysis by prolonged heating. In the presence of MAO the new zirconium, titanium, and
aluminum complexes show low activity in the polymerization of ethylene.