872332-68-8Relevant academic research and scientific papers
Low-valent titanium-pentafulvene complexes - Formation of dinuclear titanium-nitrogen complexes
Scherer, Axel,Kollak, Kay,Luetzen, Arne,Friedemann, Marion,Haase, Detlev,Saak, Wolfgang,Beckhaus, Ruediger
, p. 1003 - 1010 (2005)
Sodium amalgam reduction of [(η5-C5Me5)TiCl 3] (1) in the presence of the pentafulvenes {C5H 4=CR2, R: p-tol (2), p-FPh (3), CR2: adamantyl (4)} under nitrogen smoothly produces dark green or dark blue dinuclear low-valent titanium complexes [{(η5-C5Me 5)Ti(η6-C5H4=CR 2)}2(μ2,η1, η1-N2)] {R: p-tol (6), p-FPh (7), CR2: adamantyl (8)}, characterized by a bridging end-on coordinated dinitrogen ligand, in high yield. In the same way, the nitrogen-free, low-coordinated complex [(η5-C5Me5)Ti(η6- C9H6=C(p-tol)2)] (10) is obtained by using the more sterically demanding benzofulvene C9H6=C(P-tol) 2 (5) instead of 2-4. The solid-state structures of the dinitrogen compounds reveal weakly activated end-on bound N2 ligands with identical N-N distances of 1.160(3) A (6) and 1.160(5) A (8). The dinitrogen complexes 6, 7 and 8 show diamagnetic behaviour, which allowed a complete NMR spectroscopic characterization. So a correlation between the situation in solution, measured by NMR, and in the solid state (X-ray diffraction) becomes possible and shows a congruent picture. A broad range of reactions can be imagined concerning the easily replaceable dinitrogen ligand as well as the known reactivity of fulvene ligands in complexes of early transition metals. Wiley-VCH Verlag GmbH & Co. KGaA, 2005.
