Abstract
AbstractAddition of propylenimine (2‐methylaziridine) to the bis(cyclopentadienyl)titanium sandwich complexes, (η5‐C5Me4R)2Ti (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)2Ti(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‐C5Me4SiMe3)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 putativetitanocene ammonia complex.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
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