Addition of propylenimine (2-methylaziridine) to the bis(cyclopentadienyl) titanium sandwich complexes, (η5-C5Me 4R)2-Ti (R = iPr, SiMe3), resulted in rapid [NH] group transfer followed by C-H activation of a cyclopentadienyl methyl group to yield the corresponding cyclometalated titanocene amido compounds. Exposure of these molecules to 4 atm of H2 at 55°C resulted in hydrogenolysis of the metal-carbon bond to form the titanium amido hydride compounds, (η5-C5Me4R)2- Ti(NH2)H. Deuteriolysis with DCl gas confirmed exclusive cyclometalation from the positions adjacent to the isopropyl and trimethylsilyl substituent. Oxidative addition of the N-H bonds of amines has also been observed. Addition of NH3 to either (η5-C 5Me4SiMe3)2Ti or (η5-C5Me4iPr)2Ti yielded the corresponding titanocene amido hydrides along with the titanocene(III) amides, (η5-C5Me4R)2TiNH2, arising from formal deprotonation by unreacted sandwich from the putative titanocene ammonia complex.
All Science Journal Classification (ASJC) codes
- Inorganic Chemistry
- Group transfer
- Oxidative addition