ISSN:
1434-1948
Keywords:
Titanium
;
C-H activation
;
Amido complexes
;
Bridging imide ligands
;
Bridging imine group
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The new organometallic binuclear complexes [{Cp*Ti(NEt2)}2(μ-NEt)2] (1), [(Cp*Ti)2(NMe2)(NHMe2)(μ-NMe)(μ-NCH2)] (2), and [(Cp*TiCl)2(μ-NMe)2] (3) have been obtained by heating the dialkylamido derivatives [Cp*Ti(NR2)nCl3-n] (R = Et, n = 3; R = Me, n = 2, 3) (Cp* = η5-C5Me5) in solution and at different temperatures. The thermal decomposition of [Cp*Ti(NMe2)Cl2] at temperatures above 145 °C caused the activation of the pentamethylcyclopentadienyl ligand to give the new, geometrically constrained, complex [{η5:η1-C5Me4CH2CH2N(Me)}TiCl2] (5). Addition of the isocyanide 2,6-Me2C6H3NC to the solution obtained in this last process led to the isolation of the complex [{η5:η2-C5Me4CH2CH2N(Me)CN(C6H3Me2)}TiCl2] (6) by insertion of one isocyanide molecule into the titanium-nitrogen bond in 5. The structure of 6 has been proved by an X-ray diffraction study which showed the organic ligand, C5Me4CH2CH2N(Me)CN(C6H3Me2), to be coordinated to the titanium atom via the cyclopentadienyl ring and a η2-iminocarbamoyl fragment. Heating of the trinuclear oxo derivative [{Cp*Ti(NMe2)}3(μ-O)3] at 110 °C gave the complex [{Cp*3Ti3(NMe2)(μ-η2-CH2NMe)}(μ-O)3] (4) where an imine ligand bridges two of the three metallic centres.
Type of Medium:
Electronic Resource
Permalink