摘要
A modular synthesis of tris(aryl) tren ligands has been demonstrated via the condensation of nitrilotracetyl chloride with different anilines followed by reduction. Varying the aniline in the condensation step from 2-methylthioaniline, to 2-phenylthioaniline, to 2-chloroaniline, generates 2,2',2''-nitrilotris (N-(2-(methylthio) phenyl) acetamide) (1), 2,2',2''-nitrilotris(N-(2-(phenylthio) phenyl) acetamide) (2) and 2,2',2''-nitrilotris(N-(2-chlorophenyl) acetamide) (3) respectively. The 2-chloroaniline synthesis is complicated by the production of N-(2-chlorophenyl)-3,5-dioxo-1-piperazine-N-(2-chlorophenyl) acetamide (4), but can be adjusted to produce only 3. The reduction of complexes 1-3 proceeds with lithium aluminum hydride for 1 and 2 and with borane for 3 to yield the tris(aryl) tren ligands tris-(2-(2-(methylthio) phenylamino) ethyl) amine (5), tris-(2-(2-(phenylthio) phenylamino) ethyl) amine (6), and tris-(2-(2-chlorophenylamino) ethyl) amine (7). All three of these ligands can be deprotonated with tert-butyllithium for 5 and 7, and n-butyllithium for 6 to generate their trilithium complexes, 8, 9 and 10 for 5, 6 and 7 respectively, with 10 forming two different solvates (10a and 10b). All complexes are characterized by H-1 and C-13 NMR and the solid state structures of complexes 2, 3, 4, 7, 8, 9, 10a and 10b are described.
- 出版日期2017-5-1