Tetraamine Me₆TREN induced monomerization of alkali metal borohydrides and aluminohydrides

Monomeric 1:1 complexes of MEH4 (M, E = Li, B, 1; Na, B, 2; Li, Al, 3; Na, Al, 4) and the tripodal tetradentate ligand (Me2NCH2CH2)3N (Me6TREN) have been prepared in good yields by refluxing in THF and allowing the solutions to cool slowly. X-ray diffraction studies show that the BH4 group binds to either Li or Na via three hydride bridges while the AlH4 group connects to Li via a single hydride bridge. Surprisingly, Me6TREN·LiAlH4 represents the first monomeric contacted ion pair LiAlH4 derivative to be structurally characterized. In every case the tetraamine coordinates via all four of its Lewis basic nitrogen atoms. A similar protocol using the alkyl-rich borohydride MBEt3H also gives monomeric species (M = Li, 5; Na, 6). All complexes have been characterized in solution by multinuclear (1H, 7Li, 11B, 13C and 27Al, where appropriate) NMR spectroscopy which reveals excellent textbook examples of 1J coupling between B/Al and H in the cases of complexes 1-4 and between B and C in the cases of complexes 5 and 6.