Reversible Formation of a Cerium‐Bound Terminal Hydride: Ce(C₅Me₄SiMe₃)₂(H)(thf)

Abstract

The use of the bulky cyclopentadienyl ligand Cp′ (Cp′ = C5Me4SiMe3) to stabilize cerium hydrides has resulted in the preparation of two novel tuck‐in complexes with C–H activated SiMe3 groups. Subsequent reaction of these with H2 in thf gives a lanthanide terminal hydride species Ce(Cp′)2(H)(thf) which reversibly regenerates the tuck‐in complex under sustained vacuum. This compound is only the second structurally characterized terminal cerium hydride. This new hydride is a catalyst in H/D exchange reactions between with both sp3‐CH and sp2‐CH bonds, and for the hydrogenation of unsaturated alkene bonds.

Cerium(III) Carbonate Formation from {CeCp*2H}2 and Carbon Dioxide: Structure and Mechanistic Insights

“…13 Recently, we have been interested in the synthesis and reactivity of cerium hydrides, and have reported the preparation of a rare terminal Ce−H bond, stabilized with C 5 Me 4 SiMe 3 coligands. 14 In this work, we examine the reactivity of Ce−H bonds toward CO 2 using the known complex {CeCp* 2 H} 2 . 4…”

f-Block hydride complexes – synthesis, structure and reactivity

“…This method has advantages in its simplicity and the generation of only volatile byproducts from the transformation; however, some hydrogenolysis reactions with larger lanthanides (Ce, Nd, Sm), have been shown to be reversible-even in the solid state-necessitating handling and storage of these species under a hydrogen atmosphere. 25 Okuda et al report the synthesis of the lutetium complex [(Me 4 TACD)Lu(R) 2 ] + , which reacts with H 2 at 1 bar pressure in thf (Fig. 3).…”

“…With the very large Cp′* ligand, monomeric complexes become isolable across the series: solvated Ce, Dy and Lu examples exhibit bond lengths ranging from 2.27-2.14 Å (Ce-Lu). 25,37…”