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Imido-alkyne coupling in titanium complexes: New insights into the alkyne hydroamination reaction

Vujkovic, N., Ward, Benjamin David, Maisse-Francois, A., Wadepohl, H., Mountford, P. and Gade, L. H. 2007. Imido-alkyne coupling in titanium complexes: New insights into the alkyne hydroamination reaction. Organometallics 26 (23) , pp. 5522-5534. 10.1021/om700758v

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Titanium imido complexes [Ti(NR)(N2ArNpy)(L)] (N2ArNpy = MeC(2-C5H4N)(CH2NAr)2, Ar = 4-C6H4Me or 3,5-C6H3Me2) have been prepared from the corresponding bis(amide) complexes [Ti(N2ArNpy)(NMe2)2]. The reaction chemistry of the imido ligand has been investigated with aryl acetylenes, affording the {2 + 2} cycloaddition products [Ti(N2ArNpy){κ2-N(tBu)CHCAr‘}] (Ar‘ = Ph and 4-C6H4Me) which represent a catalytic intermediate in the anti-Markovnikov hydroamination of terminal alkynes. Reaction of these azatitanacyclobutene complexes with tert-butylamine completes the catalytic cycle, affording trans-cinnamyl(tert-butyl)amine; conversely, reaction with a second equivalent of alkyne afforded a second insertion product, an azatitanacyclohexadiene [Ti(N2ArNpy){κ2-N(tBu)CHC(Ar‘)C(Ar‘) = CH}], two examples of which have been characterized by X-ray crystallography. Studies into the catalytic hydroamination of phenyl acetylene with tert-butylamine have been performed and indicate that the formation of an azatitanacyclohexadiene complex represents a deactivation pathway in this catalytic reaction.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Subjects: Q Science > QD Chemistry
Publisher: American Chemical Society
ISSN: 0276-7333
Last Modified: 04 Jun 2017 02:08

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