Recent advances in heavy element chemistry spurred by innovative molecular design, new spectroscopic techniques, and relativistic theory have evolved our understanding of the divergence between the chemistries of 5f elements and their 4f counterparts. Historically the primary distinction between these two series has been that early actinides display facile redox chemistry compared to lanthanides with the exception of those with special electronic configurations such as Eu II (4f ) and Yb II (4f ). This key attribute is largely lost in all trans-plutonium elements (excluding nobelium) where the most stable oxidation state is 3+ akin to lanthanides. This has led to the notion that their chemistries are lanthanide-like. The combination of this bias with their scarcity, short half-lives, and need for specialized research facilities has further stymied progress in understanding these elements. However, it has been known for several decades that actinides from californium to nobelium have accessible 2+ oxidation states. In fact, electro-and thermochemical measurements have shown a progressive stabilization of the 2+ state ultimately revealing that No II is more stable than No III by 1.45 V. Of late significant efforts have been dedicated to isolating complexes containing f-elements in either new or rare oxidation states for the purpose of determining their electronic configurations, bonding trends, spectroscopic features, and reactivity. Using strong reductants such as KC8 and low-temperature reaction conditions, the first examples of Th II , U II , Np II , and Pu II triscyclopentadienyl derivatives such as [Pu(Cp')3] 1-(Cp' = trimethylsilylcyclopentadienyl) have been prepared, characterized, and their reactivities explored. These studies inspired the pursuit of other molecular scaffolds for stabilizing U II such as the U II bis(amidate arene) [U(TDA)2] 1-(TDA = N-(2,6-di-isopropylphenyl)pivalamido) that acts as U I synthon because of the non-innocence of the ligand, as well as the monoarene [U(( Ad,Me ArO)3mes)] that exhibits stabilization of U II via backbonding. These reductive methods can also yield compounds whose oxidation states are difficult to describe such as [K(18-crown-6)(THF)2]2[U(η 6 -C14H10)(η -C14H10)(μ-OMe)]2•4THF. Likewise, Cf II complexes have been prepared in the gas phase as exemplified by reductive elimination of CH3SO2 from Cf III (CH3SO2)4 -to yield Cf II (CH3SO2)3 -. The issue with applying the above synthetic methods to the preparation of low-valent transplutonium complexes is that unlike early actinides the standard reduction potential for An III → An II can be quite similar to the potential for An III → An 0 . In fact, even with uranium the reaction of UCl4 with LiC10H8 results in the formation of U 0 nanoparticles. Thus, it would be expected that the reactions of alkali metal-based reagents with Cf III should result in the formation of Cf 0 unless the supporting ligands prevent over reduction because the potential for Cf III → Cf II is -1.525 V, whereas the Cf III → Cf 0 potential is -2.01 V. Moreover, for americium the potential for Am III → Am II is -2.28 V versus Am III → Am 0 at -2.00 V, rendering the formation of Am 0 at lower energy than Am II . Reagents such as KC8 are expected to yield ca. 2.93 V of reduction potential and thus are anticipated to be too strong for preparing most trans-plutonium An II complexes.