Issue 3, 2008

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

Abstract

Heterobimetallic complexes of the general formula [{(OC)5M[double bond, length as m-dash]C(Me)OTi(OiPr)2}(µ-OiPr)]2 with M = Cr (1), W (2) were synthesized by reacting (OC)5M[double bond, length as m-dash]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[double bond, length as m-dash]C(Me)O]2Ti(OiPr)2(C5H5N)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 Cl2Ti(OiPr)2(C5H5N)2 (5) and (OC)5M[double bond, length as m-dash]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.

Graphical abstract: Titanoxycarbene complexes of Ti(iv) with O- and N-donor ligands

Supplementary files

Article information

Article type
Paper
Submitted
01 Oct 2007
Accepted
11 Dec 2007
First published
08 Jan 2008

New J. Chem., 2008,32, 540-546

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

S. D. Nogai, O. Schuster, J. Bruce and H. G. Raubenheimer, New J. Chem., 2008, 32, 540 DOI: 10.1039/B715075J

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements