Synthesis, structural and physicochemical characterization of a new type Ti6-oxo cluster protected by a cyclic imide dioxime ligand

Passadis, S. S., Hadjithoma, S., Kalampounias, A. G., Tsipis, A. C., Sproules, S. , Miras, H. N. , Keramidas, A. D. and Kabanos, T. A. (2019) Synthesis, structural and physicochemical characterization of a new type Ti6-oxo cluster protected by a cyclic imide dioxime ligand. Dalton Transactions, 48, pp. 5551-5559. (doi: 10.1039/C9DT00658C) (PMID:30785155)

Abstract

Reaction of the cyclic ligand (2Z,6Z)-piperidine-2,6-dione dioxime with TiCl4 and KOH yielded the hexanuclear cluster K6[TiIV6(μ3-O)2(μ2-O)3(CH3O)6(μ2–η1,η1,η2-Hpidiox-O,N,O′)4(μ2–η1,η1,η2-pidiox-O,N,O′)2]·7.5CH3OH possessing a new {Ti6O5} structural motif. The cluster core {Ti6O5} 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.

• Item Type: Articles
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Sproules, Dr Stephen and Moiras, Professor Haralampos
• Authors: Passadis, S. S., Hadjithoma, S., Kalampounias, A. G., Tsipis, A. C., Sproules, S., Miras, H. N., Keramidas, A. D., and Kabanos, T. A.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: Dalton Transactions
• Publisher: Royal Society of Chemistry
• ISSN: 1477-9226
• ISSN (Online): 1477-9234
• Published Online: 14 February 2019
• Copyright Holders: Copyright © 2019 The Royal Society of Chemistry
• First Published: First published in Dalton Transactions 48:5551-5559
• Publisher Policy: Reproduced in accordance with the publisher copyright policy