The synthesis and characterization of (TptBu,Me)Yb(BH4)(THF)n (n = 0, 3; n = 1, 4) complexes are reported. The compounds represent rare examples of lanthanide (II) tetrahydroborate complexes. The X-ray crystal structure of complex 4 has been determined and it shows a monomeric, formally seven coordinate ytterbium center, bearing one κ3 bonded TptBu,Me ligand, a tetrahydroborate ligand and a coordinated THF molecule. The tetrahydroborate ligand binds in a κ3 fashion, via three bridging hydrogen atoms. IR spectroscopy data are consistent with the solid-state structure and the corresponding BD4 analog of 4 shows the expected IR isotope shifts. The 1H NMR spectra of 3 and 4 shows one set of resonances each for the BH4 and the pyrazolylborate ligands indicating dynamic solution behavior. For complex 3, although X-ray quality crystals could not be obtained, the IR and NMR data are consistent with its formulation as the solvent-free analog of complex 4 with κ3-bonded BH4 ligand.Monomeric ytterbium (II) tetrahydroborate complexes supported by tris(pyrazolylborate) ligands, (TptBu,Me)Yb(BH4)(THF)0/1 were synthesized and characterized. The synthesis of (TptBu,Me)Yb(BH4)(THF) was found to depend on both solvent and alkali metal borohydride used. The synthesis proceeded optimally using NaBH4 in acetonitrile. The structure of (TptBu,Me)Yb(BH4)(THF) revealed a monomeric ytterbium (II) center in which the tetrahydroborate ligand is κ3 coordinated to the ytterbium center. A similar structure is proposed for (TptBu,Me)Yb(BH4) based on spectroscopic evidence.

The reaction of [Ln(TpMe,Me)2] (Ln=Sm, Eu, Yb) with TCNE and TCNQ gave good yields of the expected salt [Ln(TpMe,Me)2]Y (Y=TCNE, TCNQ) as a THF solvate. The crystal structure of [Yb(TpMe,Me)2][TCNE]·(THF)6 was determined and shows the expected salt-like formulation, but shows no significant interionic contacts. The reactions with TCNQ produced less well-defined products with evidence for interionic contacts.