The late 3d metals offer a significant economic advantage over their heavier counterparts and one interest has been using 3d metals for energy catalysis, including hydrocarbon functionalization. Three-coordinate late transition metal complexes are stablilzed with �-diketiminates; as an alkoxide, these complexes undergo a methathesis reaction with amines to produce metal amines and alcohol. Density functional calculations were done on a model system using B3LYP/6-31+(d), with tert-butoxide bonded to the metal and hydrogens on the �-diketiminate. The full system, with 2,6-diisopropylphenyl bonded to the nitrogens and methyls on the side carbons of the �-diketiminate, was studied using B3LYP/6-31+(d):UFF and was found to be comparable to the model system. Different substituents were placed on the �-diketiminate to determine steric and electronic effects on the free energy of activation. For these systems, the most thermodynamically favorable metals were nickel and copper. For amines, aniline was the most exergonic, followed by ammonia and then adamantylamine.

Late <i>3d</i> metal metathesis of metal-alkoxides with amines

243rd National Meeting (2012)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.

Late 3d metal metathesis of metal-alkoxides with amines