Cyclopentadienyl-hydrazido titanium complexes: Tuning of coordination modes of hydrazido ligands to the titanium center

Cyclopentadienyl−hydrazido titanium complexes [(η5-C5Me4)SiMe2(NNMe2)]TiR2 (R = NMe2 (2), Cl (3), Me (5)) and [(η5-C5Me4)SiMe2(NNMe2AlMe3)]TiMe2 (4) have been prepared and characterized. Single-crystal X-ray diffraction studies reveal that complexes 2−5 contain η1-hydrazido (2 and 4) and η2-hydrazido (3 and 5) groups depending on the electronic nature of the titanium center. The reaction of 2 with H2O produces a tetrameric organotitanoxane [(η5-C5Me4)(SiMe2NHNMe2)Ti]4O6 (6) with an adamantane-like cage structure.