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Coordination of LiH Molecules to Mo≣Mo Bonds: Experimental and Computational Studies on Mo2LiH2, Mo2Li2H4, and Mo6Li9H18 Clusters

IIQ

Marina Perez-Jimenez, Natalia Curado, Celia Maya, Jesus Campos, Jesus Jover, Santiago Alvarez and Ernesto Carmona J. Am. Chem. Soc. 2021, Vol. 143, 5222–5230

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 AdDipp2 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 (AdDipp2 = HC(NDipp)2; Dipp = 2,6-iPr2C6H3; 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(AdDipp2)] 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.

https://doi.org/10.1021/jacs.1c01602

 

 

Marina Perez