The reactions of organic azides (RN 3 ; R = 2,6-dimesitylphenyl, SiMe 3 ) with bis(η 5 :η 1 -pentafulvene)titanium complexes 1 and titanium monopentafulvene complexes [Cp # Ti(η 5 :η 1 -pentafulvene)Cl] (5; #: R 5 = H, Me) were investigated. For complexes 1, insertion of the γ-N atom of the azide into the Ti-C exo bond results in the formation of titanium triazenido complexes 2 in good yields. Complexes 2 undergo subsequent rearrangements in solution to titanium imido com- [a] [a]
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