Contributions to the Structural Chemistry of 2‐Amino Alcoholate Derivatives of Titanium and Zirconium Alkoxides and Their Partial Hydrolysis Products

The structures of Ti 2 (O i Pr) 6 (OCHMeCH 2 NH 2 ) 2 and Ti 2 (O i Pr) 6 (OCH 2 CHMeNH 2 ) 2 , obtained by reaction of Ti(O i Pr) 4 with the corresponding amino alcohols, were investigated to elucidate the structural influence of the organic substituents at the amino alcohol. A methyl group at the OH‐substituted carbon atom results in a larger distortion of the structure than a methyl group at the NH 2 ‐substituted carbon. The disubstituted compound Ti 2 (O i Pr) 4 (OCH 2 CH 2 NH 2 ) 4 was formed, when NaTi(O i Pr) 5 was reacted the amino ethanol. While one OCH 2 CH 2 NH 2 ligand is chelating, the oxygen atom of the second bridges the titanium atoms, and the NH 2 group is dangling. The structures of the partial hydrolysis products Ti 4 O 4 (O i Pr) 4 (OCHPhCHMeNHMe) 4 and Ti 8 O 6 (OEt) 12 (OCH 2 CH 2 NH 2 ) 8 were also investigated. The former contains an incomplete double‐cube Ti 4 O 4 cluster core, the latter is made of two Ti 4 O 3 (OEt) 6 (OCH 2 CH 2 NH 2 ) 4 sub‐units, with a nearly planar Ti 4 (μ 2 ‐O) 2 (μ 3 ‐O)(μ 2 ‐OEt) 2 ring system, connected by two OEt bridges. Zr(OCH 2 CH 2 NH 2 ) 4 is a mononuclear compound with four chelating amino alcoholate ligands. The structure of Zr 6 (OBu) 18 (OCH 2 CH 2 NH 2 ) 6 is assembled from two Zr 2 (OBu) 5 (OCH 2 CH 2 NH 2 ) 3 and two Zr(OBu) 4 sub‐units, which are associated by alkoxo bridges. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)