From Organic Azides through Titanium Triazenido Complexes to Titanium Imides

The reactions of organic azides (RN₃, R=2,6-dimesitylphenyl, SiMe₃) with bis(η⁵:η¹-pentafulvene)titanium complexes 1 and titanium monopentafulvene complexes Cp#Ti(η⁵:η¹-pentafulvene)Cl (5, #: R₅=H, Me) are investigated. For the bis(η⁵:η¹-pentafulvene)titanium complexes 1 an insertion of the γ-N-atom of the azide into the Ti-Cexo bond is observed, resulting in the formation of titanium triazenido complexes 2 in good yields. These triazenido complexes 2 undergo subsequent rearrangements in solution to titanium imido complexes 3 and 4 via release of N₂. Due to a haptotropic shift of the fulvene ligands, a C-C coupling of the fulvenes occurs, leading to a new chelating cyclopentadienyl allyl system. By the use of the Lewis donor 4-chlorobenzonitrile these imido complexes are stabilized. The titanium monopentafulvene complexes 5 directly generate the chloride bridged titanium imido complexes 6 via release of N₂ and the fulvene ligand. These new compounds are characterized by NMR spectroscopy and single-crystal X-ray diffraction.

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