Elucidating Solution-State Coordination Modes of Multidentate Neutral Amine Ligands with Group-1 Metal Cations: Variable-Temperature NMR Studies

[Image: see text] Multidentate neutral amine ligands play vital roles in coordination chemistry and catalysis. In particular, these ligands are used to tune the reactivity of Group-1 metal reagents, such as organolithium reagents. Most, if not all, of these Group-1 metal reagent-mediated reactions occur in solution. However, the solution-state coordination behaviors of these ligands with Group-1 metal cations are poorly understood, compared to the plethora of solid-state structural studies based on single-crystal X-ray diffraction (SCXRD) studies. In this work, we comprehensively mapped out the coordination modes with Group-1 metal cations for three multidentate neutral amine ligands: tridentate 1,4,7-trimethyl-1,4,7-triazacyclononane (Me(3)TACN), tetradentate tris[2-(dimethylamino)ethyl]amine (Me(6)Tren), and hexadentate N,N′,N″-tris-(2-N-diethylaminoethyl)-1,4,7-triaza-cyclononane (DETAN). The macrocycles in the Me(3)TACN and DETAN are identified as the rigid structural directing motif, with the sidearms of DETAN providing flexible “on-demand” coordination sites. In comparison, the Me(6)Tren ligand features more robust coordination, with the sidearms less likely to undergo the decoordinating–coordinating equilibrium. This work will provide a guidance for coordination chemists in applying these three ligands, in particular, the new DETAN ligand to design metal complexes which suit their purposes.