Variable nuclearity scorpionate-supported lanthanide polyhydrides: [(TpR,R′)LnH2]n (n = 3, 4 and 6)

The synthesis and chemistry of monoligand lanthanide dihydrides, LLnH2, is a very active current area of research. Herein we summarize the status of our contributions utilizing various scorpionates, TpR,R′, as protective ancillary ligands and show that the nuclearity of the so obtained hydride clusters depends on the size of the scorpionate ligands and, in one instance, the solvent used in the synthesis. Following brief consideration of the synthesis of the various precursor dialkyl complexes, (TpR,R′)Ln(CH2SiMe3)2(THF)1/0, the solid-state structures of the hydride clusters, [(TpR,R′)LnH2]n (R, R′ = Me, Ln = Nd, Sm, Y, Yb and Lu, n = 4; R, R′ = H, Ln = Y, Yb and Lu, n = 6; R, R′ = iPr, Ln = Y and Lu, n = 3), obtained via hydrogenolysis, are described.

Graphical abstractLanthanide polyhydrides of different sizes have been obtained by hydrogenolysis of various scorpionate anchored lanthanide dialkyl complexes, (TpR,R′)Ln(CH2SiMe3)2(THF). The nuclearity of the cluster hydrides can be controlled by judicious choice of the scorpionate ligand. The solid-state structures of the currently available [(TpR,R′)LnH2]n complexes are reviewed.Figure optionsDownload full-size imageDownload as PowerPoint slide