Actinides: Organometallic Chemistry

Abstract

An actinide organometallic complex is one containing an actinide‐carbon π‐bond, an actinide‐carbon σ‐bond, or a combination of both. Actinide organometallic complexes are known for the actinide (An) elements from thorium through californium; the vast majority of the reports on organoactinide compounds, however, deal with thorium and uranium. The latter elements have isotopes, for example, thorium‐232 ( t 1/2 = 1.41 × 10 10 years) and uranium‐238 ( t 1/2 = 4.468 × 10 9 years), with extremely long half‐lives. Modern organoactinide chemistry is characterized by the existence not only of actinide analogs to many classes of d transition metal complexes, but increasingly common reports of compounds and types of reactions unique to the actinide series.

Theoretical Studies of AnII2(C8H8)2 (An = Th, Pa, U, and Np) Complexes: The Search for Double-Stuffed Actinide Metallocenes

“…By contrast, Pa 2 (COT) 2 , U 2 (COT) 2 , and Np 2 (COT) 2 have partially filled δ and ϕ HOMOs and are not stabilized by bending. Both coaxial and bent structures are usual for actinide complexes depending upon the competition between the ligand repulsion, bond stabilization, and electron repulsion. , …”

Uranium(IV) Alkyl Complexes of a Rigid Dianionic NON-Donor Ligand: Synthesis and Quantitative Alkyl Exchange Reactions with Alkyllithium Reagents

“…These attributes have the potential to lead to organometallic reactivity inaccessible with transition-metal and lanthanide complexes, ideally resulting in new and productive applications for depleted uranium, a byproduct of nuclear isotope enrichment that is currently stockpiled in large quantities. However, the organometallic chemistry of the actinide elements, relative to that of the transition metals and lanthanides, has been slow to develop, despite very early research efforts to prepare homoleptic actinide alkyl complexes − during the Manhattan project. , Consequently, the behavior of actinide organometallic complexes in fields such as olefin polymerization, olefin hydroelementation, small-molecule (e.g., carbon dioxide) activation, chemical vapor deposition (CVD), and atomic layer deposition (ALD) remains comparatively unexplored. Furthermore, the majority of actinide alkyl chemistry has involved carbocyclic ligand complexes, in particular cyclopentadienyl and cyclooctatetraenyl complexes .…”

“…However, the organometallic chemistry of the actinide elements, relative to that of the transition metals and lanthanides, has been slow to develop, despite very early research efforts to prepare homoleptic actinide alkyl complexes − during the Manhattan project. , Consequently, the behavior of actinide organometallic complexes in fields such as olefin polymerization, olefin hydroelementation, small-molecule (e.g., carbon dioxide) activation, chemical vapor deposition (CVD), and atomic layer deposition (ALD) remains comparatively unexplored. Furthermore, the majority of actinide alkyl chemistry has involved carbocyclic ligand complexes, in particular cyclopentadienyl and cyclooctatetraenyl complexes . In contrast, actinide alkyl complexes supported by multidentate noncarbocyclic ligand anions are scarce (Figure ), despite the potential for such ligands to provide access to complexes with unique and readily tunable steric and electronic properties.…”

Divergent reactivity of [(κ3-L)ThCl2(dme)] with Grignard reagents: Alkylation, ancillary ligand transfer to magnesium, and halide exchange caught in the act

“…complexes [1]. However, non-carbocyclic ligands have recently seen a flurry of activity in this area ( Fig.…”