Hanna Tamara E, Lobkovsky Emil, Chirik Paul J
Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, NY 14853, USA.
J Am Chem Soc. 2004 Nov 17;126(45):14688-9. doi: 10.1021/ja045884r.
The activation of dinitrogen by titanium sandwich complexes of the general form (eta5-C5Me4R)2Ti (R = CHMe2, CMe3, SiMe3) has been systematically investigated. Low-temperature, in situ, solution infrared spectroscopy has allowed detection of monomeric bis-dinitrogen complexes of titanium that are isostructural with more familiar dicarbonyl derivatives. One example, (eta5-C5Me4CHMe2)2Ti(N2)2, has also been characterized by X-ray diffraction and reveals weakly activated dinitrogen ligands. From the solution IR data, the relative azophilicity of the titanium sandwich complexes has been established and increases with smaller cyclopentadienyl substituents.