Divalent metallocenes of the lanthanides - a guideline to properties and reactivity

Since the discovery in the early 1980s, the soluble divalent metallocenes of lanthanides have become a steadily growing field in organometallic chemistry. The predominant part of the investigation has been performed with samarium, europium, and ytterbium, whereas only a few reports dealing with other rare earth elements were disclosed. Reactions of these metallocenes can be divided into two major categories: (1) formation of Lewis acid-base complexes, in which the oxidation state remains +II; and (2) single electron transfer (SET) reductions with the ultimate formation of Ln(III) complexes. Due to the increasing reducing character from Eu(II) over Yb(II) to Sm(II), the plethora of literature concerning redox reactions revolves around the metallocenes of Sm and Yb. In addition, a few reactivity studies on Nd(II), Dy(II) and mainly Tm(II) metallocenes were published. These compounds are even stronger reducing agents but significantly more difficult to handle. In most cases, the metals are ligated by the versatile pentamethylcyclopentadienyl ligand: (C₅Me₅). Other cyclopentadienyl ligands are fully covered but only discussed in detail, if the ligand causes differences in synthesis or reactivity. Thus, the focus lays on three compounds: [(C₅Me₅)₂Sm], [(C₅Me₅)₂Eu] and [(C₅Me₅)₂Yb] and their solvates. We discuss the synthesis and physical properties of divalent lanthanide metallocenes first, followed by an overview of the reactivity rendering the full potential of these versatile reactants.