Two‐ and Three‐Dimensional Coordination Polymers From the Reaction of Bis‐ and Tris(2‐aminoethyl)amine with Titanium and Zirconium Alkoxides

The reaction of bis(2‐aminoethyl)amine with M(O i Pr) 4 (M = Ti, Zr) affords the chain‐like coordination polymers [M 2 (O i Pr) 8 (H 2 NCH 2 CH 2 NHCH 2 CH 2 NH 2 )] ∞ , where only the NH 2 groups of the amine are coordinated to the M 2 (O i Pr) 8 units. 2D NMR spectroscopy shows that the adducts dissociate into the starting compounds when dissolved in CD 2 Cl 2 but are slowly re‐formed in solution over a period of two weeks. Puckered layers of condensed six‐membered rings of [Ti 2 (O i Pr) 8 ] 3 [N(CH 2 CH 2 NH 2 ) 3 ] 2 are formed when [Ti(O i Pr) 4 ] is treated with tris(2‐aminoethyl)amine. The voids in the center of the rings are filled by non‐coordinated Ti 2 (O i Pr) 8 guest molecules. In contrast, chains of [Zr 2 (O i Pr) 8 (H 2 NCH 2 CH 2 NR′CH 2 CH 2 NH 2 )] {R′ = CH 2 CH 2 NH 2 [Zr 2 (O i Pr) 8 (HO i Pr)]} are formed upon treatment of tris(2‐aminoethyl)amine with [Zr(O i Pr) 4 ].(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)