Structural Investigation of Pyridinecarboxylato Titanium(IV) Complexes: An Uncommon Monomeric Octacoordinated Complex vs. a Hexaprismatic Architecture

We report the synthesis and structural characterisation of two titanium(IV) complexes. A new titanium(IV) complex bearing four picolinato ligands, denoted as Ti(pic) 4 , has been prepared under solvothermal conditions. This complex identified by single‐crystal diffraction is a new example of an octacoordinated environment for titanium(IV) and is close to an ideal triangular dodecahedron. A second synthesis of a hexaprismatric carboxylato titanium complex formulated as [Ti 6 (μ 3 ‐O) 6 (O i Pr) 6 (μ‐O 2 CC 5 H 3 NCOO i Pr) 6 ] starting from a dissymmetric anhydride pyridine carboxylic precursor is described. The solid‐state analysis shows the presence of a single compound among 13 possible species. Calculations gave evidence of a highly selective mechanism leading to the formation of the final product.