Intramolecular Aminoalkene Hydroamination Catalyzed by Magnesium Complexes Containing Multidentate Phenoxyamine Ligands

The magnesium complexes (L2MgPr)-Pr-i (L-2 = 4-tert-butyl-6-(triphenylsilyl)-2-[bis((3-(dimethylamino)propyl)amino)methyl]phenoxyl) and (LMgPr)-Mg-3-Pr-i (L-3 = 4-tert-butyl-6-(triphenylsilyl)-2-[benzyl((3-(dimethylamino)propyl)amino)methyl]phenoxyl) supported by potentially tetradentate and tridentate triphenylsilyl-substituted phenoxyamine ligands have been prepared and fully characterized. The X-ray crystallographic analysis of (LMgPr)-Mg-2-Pr-i confirmed a monomeric structure in which only one of the amine side arms is bound to the four-coordinate magnesium atom. The free and coordinated side arms in (LMgPr)-Mg-2-Pr-i undergo an exchange process at 25 degrees C in solution, while the phenoxydiamine complex (LMgPr)-Mg-3-Pr-i, on the other hand, shows no sign of fluxionality. Both complexes, as well as (LMgPr)-Mg-1-Pr-i (L-1 = 4,6-di-tert-butyl-2-[bis((3-(dimethylamino)propyl)amino)methyl]phenoxyl), were shown to be competent catalysts in the cyclization of aminoalkenes. (LMgPr)-Mg-2-Pr-i exhibited the best catalytic activity, and both triphenylsilyl-substituted complexes display zero-order rate dependence on substrate concentration and first-order rate dependence on catalyst concentration, whereas the sterically less hindered complex (LMgPr)-Mg-1-Pr-i exhibits second-order rate dependence on substrate concentration. No Schlenk-type ligand redistributions were observed, and the catalytically active magnesium species was stable after prolonged heating to 120 degrees C, according to an NMR spectroscopic study.