Novel aspects of the transamination reaction between Ti(NMe2)4 and primary amines
作者： Christian Lorber , Laure Vendier
DOI: 10.1039/C3DT50840D
关键词: Pyridine 、 Dimer 、 Crystal structure 、 Trimer 、 Deprotonation 、 Medicinal chemistry 、 Amine gas treating 、 Tautomer 、 Chemistry 、 Stereochemistry 、 Yield (chemistry) 、 Inorganic chemistry
摘要: A detailed study of the transamination reaction between Ti(NMe2)4 and primary amines RNH2 is reported Alkylamines (1-adamantylamine, t-butylamine) triphenylsilylamine yield dimers type [Ti(μ-NR)(NMe2)2]2 (R = 1-adamantyl (1), (t)Bu (2), SiPh3 (3)). The experimental conditions nature amine are important issues that determine scope reaction. When reacted under same conditions, aniline PhNH2 does not expected dimer, but instead trimer [Ti3(μ(2)-NPh)3(μ(3)-NPh)(NMe2)4(NHMe2)] (5) tetramer [Ti4(μ-NPh)5(NMe2)6] (6) complexes were characterized. 2,6-diisopropylaniline (Ar*NH2) essentially an equilibrium great complexity in which multiple species can coexist solution. However, certain circumstances, we able to isolate and/or characterize several new 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)(=NAr*)] (11), Ti(NHAr*)4 (12), [(Ar*NH)2Ti(μ-NAr*)2Ti(NMe2)(NHAr*)] (13). Complexes 8 11 tautomers. Alternatively, complex 7 was prepared by deprotonation NHMe2 ligands Ti(=NAr*)Cl2(NHMe2)2 with KN(SiMe3)2. Addition pyridine (py) Ti(NMe2)4/Ar*NH2 mixtures or allows characterization transient [Ti(μ-NAr*)(NMe2)2]2·py (14) trapping intermediates [(Me2N)(py)2Ti(μ-NAr*)2Ti(NMe2)(=NAr*)] (15), Ti(=NAr*)(NHAr*)(NMe2)(py)2 (16), Ti(=NAr*)(NHAr*)2(py)2 (17). crystal structures 15 compounds determined X-ray diffraction studies.
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