The structural chemistry of titanium alkoxide derivatives with OH-substituted bidentate ligands

Abstract

The organically modified titanium alkoxides Ti2(Oi-Pr)4(OOCCMe2O)2(i-PrOH)2 and Ti4(Oi-Pr)4(SA)6 were obtained from the reaction of Ti(Oi-Pr)4 with 2-hydroxy-isobutyric acid and salicyladoxime (SA-H2), respectively. Reaction of 1,3-dibenzoyl acetone (DBA-H) did not result in a substituted titanium alkoxide derivative, but instead in the oxo cluster Ti4O2(Oi-Pr)8(DBA)2 after allowing moisture to diffuse into the reaction mixture. The three titanium compounds show common structural features which are different to derivatives void of ligand OH groups. The latter play a decisive role in coordinating the ligands to the titanium centers. Graphic abstract

Titanium‐Oxo Clusters with Bi‐ and Tridentate Organic Ligands: Gradual Evolution of the Structures from Small to Big

“…In this cluster, the triolato ligands influence the cluster core structure to a much higher degree than the carboxylato ligands. This is indicated by the fact that Ti 4 O 2 (O i Pr) 8 [OC(Ph)CHC(O)CHC(Ph)O] 2 [36] has the same structure, with four terminal O i Pr groups in place of the two bridging carboxylato ligands (the triketonato ligand is only a di‐anion).…”

Structural Chemistry of Titanium (IV) Oxo Clusters, Part 2: Clusters without Carboxylate or Phosphonate Ligands

“…The double‐cube structure, with octahedral [TiO 6 ] building blocks, can only be retained with ligands not only balancing the charges but also filling the emptied coordination sites. This is the case for Ti 4 O 2 (O i Pr) 8 [PhC(O)CHC(O)CHC(O)Ph] 2 (Figure 4, left) [36] . The outer oxygen atoms of each triketonato ligand take the place of two terminal OR, and the inner oxygen bridges two titanium atoms.…”

“…This is the case for Ti 4, left). [36] The outer oxygen atoms of each triketonato ligand take the place of two terminal OR, and the inner oxygen bridges two titanium atoms.…”