Coordination of LiH Molecules to Mo≣Mo Bonds: Experimental and Computational Studies on Mo(2)LiH(2), Mo(2)Li(2)H(4), and Mo(6)Li(9)H(18) Clusters

[Image: see text] The reactions of LiAlH(4) 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-(i)Pr(2)C(6)H(3); thf = tetrahydrofuran, C(4)H(8)O). 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 [Mo(2){HLi(thf)H}(3)(Ad(Dipp2))] molecular architecture led to spontaneous trimerization and the formation of a chiral, hydride-rich Mo(6)Li(9)H(18) supramolecular organization that is robust enough to withstand the substitution of lithium-solvating molecules of tetrahydrofuran by pyridine or 4-dimethylaminopyridine.