Coordination of LiH Molecules to Mo≣Mo Bonds: Experimental and Computational Studies on Mo₂LiH₂, Mo₂Li₂H₄, and...

The reactions of LiAlH₄ as the source of LiH with complexes that contain (H)Mo≣Mo and (H)Mo≣Mo(H) cores stabilized by the coordination of bulky Ad^Dipp2 ligands result in the respective coordination of one and two molecules of (thf)LiH, with the generation of complexes exhibiting one and two HLi(thf)H ligands extending across the Mo≣Mo bond (Ad^Dipp2 = HC(NDipp)₂; Dipp = 2,6-Pr₂C₆H₃; thf = tetrahydrofuran, C₄H₈O). A theoretical study reveals the formation of Mo-H-Li three-center-two-electron bonds, supplemented by the coordination of the Mo≣Mo bond to the Li ion. Attempts to construct a [Mo₂{HLi(thf)H}₃(Ad^Dipp2)] molecular architecture led to spontaneous trimerization and the formation of a chiral, hydride-rich Mo₆Li₉H₁₈ supramolecular organization that is robust enough to withstand the substitution of lithium-solvating molecules of tetrahydrofuran by pyridine or 4-dimethylaminopyridine.