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(OiPr)(4) (M= Ti, Zr) affords the chain-like coordination polymers [M-2(Oipr)(8)(-)(H2NCH2CH2NHCH2CH2NH2)]infinity where only the NH2 groups of the amine are coordinated to the M2(OiPr)B units. 2D NMR spectroscopy shows that the adducts dissociate into the starting compounds when dissolved in CD2Cl2 but are slowly re-formed in solution over a period of two weeks. Puckered layers of condensed six-membered rings of [Ti-2(OiPr)(8)](3)[N(CH2CH2NH2)(3)](2) are formed when [Ti(OiPr)(4)] is treated with tris(2-aminoethyl)amine. The voids in the center of the rings are filled by non-coordinated Ti-2(OiPr)(8) guest molecules. In contrast, chains of [Zr-2(OiPr)(8)(-)(H2NCH2CH2NR'CH2CH2NH2)] {R'=CH2CH2NH2[Zr-2(OiPr)(8)(-)(HOiPr)] are formed upon treatment of tris(2-aminoethyl)amine with [Zr(OiPr)(4)]. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007).