Pentamethylcyclopentadienyl and bis(trimethylsilyl)amido complexes of the di- and trivalent lanthanides

The reaction of the divalent iodides YbI/sub 2/ and EuI/sub 2/ with NaN(SiMe/sub 3/)/sub 2/ has provided pentane-soluble, monomeric derivatives of the divalent lanthanides. These compounds are isolated as the solvated species Eu(N(SiMe/sub 3/)/sub 2/)/sub 2/L/sub 2/ (L = thf or 1,2-dme), Yb(N(SiMe/sub 3/)/sub 2/)/sub 2/(thf)/sub 1/ /sub 5/ and Yb(N(SiMe/sub 3/)/sub 2/)/sub 2/L/sub 2/ (L = 1,2-dme or OEt/sub 2/), or as the sodium salts NaM(N(SiMe/sub 3/)/sub 2/)/sub 3/ (M = Eu or Yb). The pentamethylcyclopentadienyl ligand has been used to obtain trivalent derivatives of the type (C/sub 5/Me/sub 5/)/sub 2/MCl/sub 2/M'L/sub x/ (M = Nd, Sm or Yb; M' = Li or Na; L = OEt/sub 2/ or tmed) or (C/sub 5/Me/sub 5/)/sub 2/MCl(thf) (M = Nd or Yb). These compounds undergo metathesis reactions. The interaction of NaC/sub 5/Me/sub 5/ with EuCl/sub 3/ yields only the divalent (C/sub 5/Me/sub 5/)/sub 2/EuL (L = thf or OEt/sub 2/). Analogous compounds of ytterbium are obtained by reaction of YbI/sub 2/ with NaC/sub 5/Me/sub 5/ in thf or OEt/sub 2/. The ytterbium amine complexes are weakly paramagnetic, apparently due to charge transfer from ytterbium to the aromatic rings. The divalent phosphine complexes (C/sub 5/Me/sub 5/)/sub 2/ML (M = Eu or Yb; L = dmpe or dmpm) are also described. Crystallographic data are summarized.