We have used Schlenk techniques to synthesize a family of non-classical early Ln(II) complexes stabilized by three Cp tt ligands. The steric bulk of the tris-Cp tt framework has currently limited the synthesis of Ln(III) Cp tt precursors and thus this reductive chemistry to the large early Ln, and new synthetic protocols would need to be developed to extend this series to the smaller, late Ln ions. The series of [Ln(Cp tt )3] -anions reported herein are thermally sensitive and require strictly anaerobic conditions for their isolation. Despite these issues, we have obtained solid state structures and spectral data for these complexes, which are now part of a growing body of work showing that alkylsubstituted Cp R ligands can stabilize complexes containing non-classical Ln(II) ions sufficiently to allow their isolation. The characterization data and ab initio calculations of [Ln(Cp tt )3] -anions are consistent with formal Ln(II) centers and 4f n 5d 1 ground states, in common with literature examples of [Ln(Cp R )3] -anions. 9,10