Abstract
Titanocene neopentyl complexes with one cyclometallated tert-butylcyclopentadienyl group, (η 5-C 5H 4R)(η 5,η 1-C 5H 4CMe 2CH 2)Ti(CHCMe 3), are readily obtained from the corresponding titanocene dichlorides and bis(neopentyl)magnesium. These compounds lose neopentane by α-H abstraction from the cyclometallated ligand to generate alkylidene species in which the alkylidene moiety is connected to one of the cyclopentadienyl ligands. The alkylidene (C 5H 4Me)(C 5H 4CMe 2CH)Ti(PMe 3) reacts with benzene-d 6 by stereoselective addition of a CD bond across the TiC bond. These ‘tucked-in’ alkylidene species also exhibit a wide range of reactivity towards unsaturated substrates (alkynes, ethene, benzonitrile), initiated by cycloaddition to the TiC bond.
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