Controlling Al-M Interactions in Group 1 Metal Aluminyls (M = Li, Na, and K). Facile Conversion of Dimers to Monomeric and Separated Ion Pairs

The aluminyl compounds [M{Al(NONDipp)}](2) (NONDipp = [O(SiMe(2)NDipp)(2)](2-), Dipp = 2,6-iPr(2)C(6)H(3)), which exist as contacted dimeric pairs in both the solution and solid states, have been converted to monomeric ion pairs and separated ion pairs for each of the group 1 metals, M = Li, Na, and K. The monomeric ion pairs contain discrete, highly polarized Al-M bonds between the aluminum and the group 1 metal and have been isolated with monodentate (THF, M = Li and Na) or bidentate (TMEDA, M = Li, Na, and K) ligands at M. The separated ion pairs comprise group 1 cations that are encapsulated by polydentate ligands, rendering the aluminyl anion, [Al(NONDipp)]- "naked". For M = Li, this structure type was isolated as the [Li(TMEDA)(2)](+) salt directly from a solution of the corresponding contacted dimeric pair in neat TMEDA, while the polydentate [2.2.2]cryptand ligand was used to generate the separated ion pairs for the heavier group 1 metals M = Na and K. This work shows that starting from the corresponding contacted dimeric pairs, the extent of the Al-M interaction in these aluminyl systems can be readily controlled with appropriate chelating reagents.