Synthesis, structural and physicochemical characterization of a new type Ti6-oxo cluster protected by a cyclic imide dioxime ligand. Issue 17 (20th February 2019)

• Record Type: Journal Article
• Authors: Passadis, Stamatis S.; Hadjithoma, Sofia; Kalampounias, Angelos G.; Tsipis, Athanassios C.; Sproules, Stephen; Miras, Haralampos N.; Keramidas, Anastasios D.; Kabanos, Themistoklis A.
• Is Part Of: Dalton transactions. Volume 48:Issue 17(2019)
• Page Start: 5551
• Page End: 5559
• Publication Date: 2019-02-20
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c9dt00658c
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : A new type of Ti6 -oxo cluster with a structural motif TiIV6O5 was synthesized of which the cyclo -Ti3 metallic cores exhibit metallaromaticity. Abstract : Reaction of the cyclic ligand (2 Z, 6 Z )-piperidine-2, 6-dione dioxime with TiCl4 and KOH yielded the hexanuclear cluster K6 [TiIV6(μ3 -O)2 (μ2 -O)3 (CH3 O)6 (μ2 –η 1, η 1, η 2 -Hpidiox- O, N, O ′)4 (μ2 –η 1, η 1, η 2 -pidiox- O, N, O ′)2 ]·7.5CH3 OH possessing a new {Ti6 O5 } structural motif. The cluster core {Ti6 O5 } is wrapped by external tripodal imide dioxime ligands, showing good solubility and stability and thus, allowing its solution to be studied by means of electrospray ionization mass spectrometry, electrochemistry and 2D NMR, c. w. EPR and UV-vis spectroscopies. Density Functional Theory (DFT) calculations reveal that the cyclo -Ti3 metallic cores exhibit metallaromaticity which is expected to contribute to the stabilization of this system.