Titanoxycarbene complexes of Ti(IV) with O- and N-donor ligands

Nogai S.D. ; Schuster O. ; Bruce J. ; Raubenheimer H.G. (2008)


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.

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