Titanoxycarbene complexes of Ti(IV) with O- and N-donor ligands
Date
2008
Authors
Nogai S.D.
Schuster O.
Bruce J.
Raubenheimer H.G.
Journal Title
Journal ISSN
Volume Title
Publisher
Abstract
Heterobimetallic complexes of the general formula [{(OC) 5M=C(Me)OTi(OiPr)2}(μ-OiPr)]2 with M = Cr (1), W (2) were synthesized by reacting (OC)5M=C(Me)OLi (M = Cr, W) with ClTi(OiPr)3. X-Ray crystallography revealed dimeric molecular structures based on four-membered Ti2O2-rings for both compounds. Most intriguingly crystals of 1 virtually "shattered" upon cooling below -60°C. Treatment of 1 and 2 with an excess of pyridine did not effect symmetric cleavage of the dimers, but afforded the unique rearrangement products [(OC)5M=C(Me)O]2Ti(OiPr)2(C 5H5N)2 with M = Cr (3) and W (4). The isomorphous structures, determined by means of X-ray diffraction, are only the second examples of an unrestrained titanium center coordinated by four OR and two N-donor ligands. Complexes 3 and 4 were also accessible from Cl 2Ti(OiPr)2(C5H5N)2 (5) and (OC)5M=C(Me)OLi. Owing to the inherent dynamic behaviour of all complexes, low-temperature NMR studies were undertaken. The formation of nanoparticles upon thermolysis of complex 2 lends support to the notion that the presented (or related) compounds could be useful as single source precursors for nano-sized mixed metal oxides or oxo nitrides. © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.
Description
Keywords
titanium, titanoxycarbene, unclassified drug, article, carbon nuclear magnetic resonance, chemical reaction, chemical structure, priority journal, proton nuclear magnetic resonance, synthesis, X ray diffraction
Citation
New Journal of Chemistry
32
3
32
3