Exploring the reductive CO fixation with amines and hydrosilanes using readily available Cu() NHC-phenolate catalyst precursors

N -Methylation of amines is of great interest in the synthesis of pharmaceuticals and valuable compounds, and the possibility to perform this reaction with an inexpensive and non-toxic substrate like CO 2 and its derivatives is quite appealing. Herein, the synthesis of four novel homoleptic Cu( ii ) complexes with hybrid NHC-phenolate (NHC = N -Heterocyclic Carbene) ligands is reported, and their use in the catalytic N -methylation of amines with CO 2 in the presence of hydrosilanes is explored. Both bidentate or tetradentate ligands can be used in the preparation of the complexes provided that the structural requirement that the two NHC and the two phenolate donors in the metal coordination sphere are mutually in trans is fulfilled. A new reaction protocol to perform the N -methylation of secondary aromatic amines and dibenzylamine in high yield under mild reaction conditions is developed, using the ionic liquid [BMMIM][NTf 2 ] (1-butyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide) as solvent and the catalyst precursor [Cu(L 2 ) 2 ] . Reactivity studies indicate that the reaction follows two different pathways with different hydrosilanes, and that the starting Cu( ii ) complexes are reduced under the catalytic conditions. Readily available Cu( ii ) organometallic catalyst precursors allow the N -methylation of amines with CO 2 and hydrosilanes to be efficiently performed.