Molecular Ln(III)−H−E(II) Linkages (Ln=Y, Lu; E=Ge, Sn, Pb)

Abstract

Following the alkane‐elimination route, the reaction between tetravalent aryl tintrihydride Ar*SnH3 and trivalent rare‐earth‐metallocene alkyls [Cp*2Ln(CH{SiMe3}2)] gave complexes [Cp*2Ln(μ‐H)2SnAr*] implementing a low‐valent tin hydride (Ln=Y, Lu; Ar*=2,6‐Trip2C6H3, Trip=2,4,6‐triisopropylphenyl). The homologous complexes of germanium and lead, [Cp*2Ln(μ‐H)2EAr*] (E = Ge, Pb), were accessed via addition of low‐valent [(Ar*EH)2] to the rare‐earth‐metal hydrides [(Cp*2LnH)2]. The lead compounds [Cp*2Ln(μ‐H)2PbAr*] exhibit H/D exchange in reactions with deuterated solvents or dihydrogen.

A Lead-μ2-Tetrylide Complex with Osmium(IV) Terminal Components

“…Hydrides are found in the base along with the lead atom. The latter is very far from the hydrides (>2.56(4) or 2.64 Å in the density functional theory (DFT)-optimized structure) . The absence of any Pb–H interaction was further confirmed by an AIM approach.…”

f-Block hydride complexes – synthesis, structure and reactivity

“…121 The Anwander group have gone on to expand the scope of Ln⋯H–E complexes, providing examples with E = Ge, Sn and Pb. 114 In NBO calculations based on their data, they found increasing importance of a direct Ln–E interaction upon moving from Pb to Ge, while the Ln–H bond concurrently lengthens. The bonding, therefore, may be intermediate between that of group 13 and that of group 15 complex [Cp 3 Dy-As(H) 2 Mes], which contains only a Dy–As bond (Fig.…”

“…15). 113,114 Borohydrides 108 Complexes of lanthanides with tetrahydroborate ligands-both Ln(II) and Ln(III)-are myriad in the literature, 112 owing in part…”