3 years ago

Reactions of Secondary Allylamines with Bis(η5:η1-pentafulvene)titanium Complexes: Selective Formation of Monoazabutadiene Titanium Complexes by N–H and C–H Bond Activation

Reactions of Secondary Allylamines with Bis(η5:η1-pentafulvene)titanium Complexes: Selective Formation of Monoazabutadiene Titanium Complexes by N–H and C–H Bond Activation
Marc Schmidtmann, Manfred Manßen, Jens-Henning Bölte, Iris Töben, Rüdiger Beckhaus, Christoph Kahrs
The N–H and C–H bond activation reactions at ambient conditions of seven different secondary allyl amines (Aag) with bis(η51-pentafulvene)titanium complexes (1) have been investigated. Bis(η51-adamantylidenepentafulvene)titanium (1a) reacts with N-allylaniline (Aa), N-allylbenzylamine (Ac), N-allyl-tert-butylamine (Ad), N-allylcyclohexylamine (Ae), and N-allyl-2-methylaniline (Af) to give the 1-azabutadiene complexes 2a,cf with high yields. They are the first complexes of the CH2-terminated monoazadiene RN═CHCH═CH2. Using bis(η51-di-p-tolylpentafulvene)titanium (1b), which exhibits a less Brønsted basic Cexo center, and Aa, the β-C–H bond activation can be slowed down so much that the agostic interaction between the titanium center and the C–H bond is detectable via NMR measurements at room temperature. In the reactions of the titanium azabutadiene complexes 2a,b and 3a with carbon monoxide a ligand exchange is observed, forming the titanocene dicarbonyls 4a,b.

Publisher URL: http://dx.doi.org/10.1021/acs.organomet.7b00425

DOI: 10.1021/acs.organomet.7b00425

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