Synthetic strategies to yield molecular complexes of high-valent lanthanides, other than the ubiquitous Ce 4+ ion, are exceptionally rare, and thorough, detailed characterization in these systems is limited by complex lifetime and reaction and isolation conditions. The synthesis of high-symmetry complexes in high purity with significant lifetimes in solution and the solid state is essential for determining the role of ligand-field splitting, multiconfigurational behavior, and covalency in governing the reactivity and physical properties of these potentially technologically transformative tetravalent ions. We report the synthesis and physical characterization of an S 4 symmetric, fourcoordinate tetravalent terbium complex, [Tb(NP(1,2-bis-t Budiamidoethane)(NEt 2 )) 4 ] (where Et is ethyl and t Bu is tert-butyl). The ligand field in this complex is weak and the metal− ligand bonds sufficiently covalent so that the tetravalent terbium ion is stable and accessible via a mild oxidant from the anionic, trivalent, terbium precursor, [(Et 2 O)K][Tb(NP(1,2-bis-t Bu-diamidoethane)(NEt 2 )) 4 ]. The significant stability of the tetravalent complex enables its thorough characterization. The stepwise development of the supporting ligand points to key ligand control elements for further extending the known tetravalent lanthanide ions in molecular complexes. Magnetic susceptibility, electron paramagnetic resonance (EPR) spectroscopy, X-ray absorption near-edge spectroscopy (XANES), and density functional theory studies indicate a 4f 7 ground state for [Tb(NP(1,2-bis-t Bu-diamidoethane)(NEt 2 )) 4 ] with considerable zero-field splitting, demonstrating that magnetic, tetravalent lanthanide ions engage in covalent metal−ligand bonds. This result has significant implications for the use of tetravalent lanthanide ions in magnetic applications since the observed zero-field splitting is intermediate between that observed for the trivalent lanthanides and for the transition metals. The similarity of the multiconfigurational behavior in the ground state of [Tb(NP(1,2-bis-t Bu-diamidoethane)(NEt 2 )) 4 ] (measured by Tb L 3 -edge XAS) to that observed in TbO 2 implicates ligand control of multiconfigurational behavior as a key component of the stability of the complex.

The homoleptic complexes of cerium with the tris­(piperidinyl)­imidophosphorane ligand, [NP­(pip)3]−, present the most negative Ce3+/4+ redox couple known (<−2.64 V vs Fc/Fc+). This dramatic stabilization of the cerium tetravalent oxidation state [>4.0 V shift from the Ce3+/4+ couple in 1 M HClO4(aq)] is established through reactivity studies. Spectroscopic studies (UV–vis, electron paramagnetic resonance, and Ce L3-edge X-ray absorption spectroscopy), in conjunction with density functional theory studies, reveal the dominant covalent metal–ligand interactions underlying the observed redox chemistry and the dependence of the redox potential on the binding of potassium in the inner coordination sphere.

The thermochemistry, descriptive chemistry, spectroscopy, and physical properties of the tetravalent lanthanides (Pr, Nd, Tb and Dy) in extended phases, gas phase, solution, and as isolable molecular complexes are presented.