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Issue 34, 2013
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Novel aspects of the transamination reaction between Ti(NMe2)4 and primary amines

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Abstract

A detailed study of the transamination reaction between Ti(NMe2)4 and primary amines RNH2 is reported Alkylamines (1-adamantylamine, t-butylamine) and triphenylsilylamine yield dimers of the type [Ti(μ-NR)(NMe2)2]2 (R = 1-adamantyl (1), tBu (2), SiPh3 (3)). The experimental conditions and the nature of the amine are important issues that determine the scope and yield of the reaction. When reacted under the same conditions, aniline PhNH2 does not yield the expected dimer, but instead the trimer [Ti32-NPh)33-NPh)(NMe2)4(NHMe2)] (5) and tetramer [Ti4(μ-NPh)5(NMe2)6] (6) complexes were characterized. The reaction of Ti(NMe2)4 and 2,6-diisopropylaniline (Ar*NH2) is essentially an equilibrium reaction of great complexity in which multiple species can coexist in solution. However, under certain circumstances, we were able to isolate and/or characterize several new complexes such as [Ti(μ-NAr*)(NMe2)2]2 (7), [(Me2N)2Ti(μ-NAr*)2Ti(NMe2)(NHAr*)] (8), [Ti(NMe2)3]2(μ-NAr*) (9), [(Ar*NH)2Ti(μ-NAr*)2Ti(NMe2)2] (10), [(Me2N)(Me2NH)Ti(μ-NAr*)2Ti(NMe2)([double bond, length as m-dash]NAr*)] (11), Ti(NHAr*)4 (12), and [(Ar*NH)2Ti(μ-NAr*)2Ti(NMe2)(NHAr*)] (13). Complexes 8 and 11 are tautomers. Alternatively, complex 7 was prepared by deprotonation of NHMe2 ligands in Ti([double bond, length as m-dash]NAr*)Cl2(NHMe2)2 with KN(SiMe3)2. Addition of pyridine (py) to the reaction of Ti(NMe2)4/Ar*NH2 mixtures or to 7 or 8 allows characterization of transient [Ti(μ-NAr*)(NMe2)2]2·py (14) and trapping of the intermediates [(Me2N)(py)2Ti(μ-NAr*)2Ti(NMe2)([double bond, length as m-dash]NAr*)] (15), Ti([double bond, length as m-dash]NAr*)(NHAr*)(NMe2)(py)2 (16), and Ti([double bond, length as m-dash]NAr*)(NHAr*)2(py)2 (17). The crystal structures of 15 compounds were determined by X-ray diffraction studies.

Graphical abstract: Novel aspects of the transamination reaction between Ti(NMe2)4 and primary amines

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Publication details

The article was received on 28 Mar 2013, accepted on 03 Jun 2013 and first published on 10 Jul 2013


Article type: Paper
DOI: 10.1039/C3DT50840D
Citation: Dalton Trans., 2013,42, 12203-12219

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    Novel aspects of the transamination reaction between Ti(NMe2)4 and primary amines

    C. Lorber and L. Vendier, Dalton Trans., 2013, 42, 12203
    DOI: 10.1039/C3DT50840D

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