Insight into the Structural Ambiguity of Actinide(IV) Oxalate Sheet Structures: A Case for Alternate Coordination Geometries.

Invited for the cover of this issue is the group of Amy Hixon at the University of Notre Dame. The image depicts the newly identified structure of a PuIV oxalate sheet compared to the historically assumed structure. Read the full text of the article at 10.1002/chem.202301164.

Insight into the Structural Ambiguity of Actinide(IV) Oxalate Sheet Structures: A Case for Alternate Coordination Geometries.

Plutonium(IV) oxalate hexahydrate (Pu(C2 O4 )2 ⋅ 6 H2 O; PuOx) is an important intermediate in the recovery of plutonium from used nuclear fuel. Its formation by precipitation is well studied, yet its crystal structure remains unknown. Instead, the crystal structure of PuOx is assumed to be isostructural with neptunium(IV) oxalate hexahydrate (Np(C2 O4 )2 ⋅ 6 H2 O; NpOx) and uranium(IV) oxalate hexahydrate (U(C2 O4 )2 ⋅ 6 H2 O; UOx) despite the high degree of unresolved disorder that exists when determining water positions in the crystal structures of the latter two compounds. Such assumptions regarding the isostructural behavior of the actinide elements have been used to predict the structure of PuOx for use in a wide range of studies. Herein, we report the first crystal structures for PuOx and Th(C2 O4 )2 ⋅ 6 H2 O (ThOx). These data, along with new characterization of UOx and NpOx, have resulted in the full determination of the structures and resolution of the disorder around the water molecules. Specifically, we have identified the coordination of two water molecules with each metal center, which necessitates a change in oxalate coordination mode from axial to equatorial that has not been reported in the literature. The results of this work exemplify the need to revisit previous assumptions regarding fundamental actinide chemistry, which are heavily relied upon within the current nuclear field.

Computational investigations of Dienes defect- and vacancy-induced changes in the electronic and vibrational properties of carbon fiber structural units.

Carbon fiber (CF) is a promising lightweight alternative to steel and is of significant interest for energy applications. As CF continues to find new uses and is exposed to new external conditions, a noninvasive method of monitoring its structural integrity is critical. Raman spectroscopy is a commonly used method for this monitoring; however, it is highly inferential, and the interpretation of the data is not always straightforward. In this work, we perform density functional theory (DFT) calculations to investigate changes in the vibrational properties of CF structural units (i.e., graphene and graphite) caused by monovacancy and Dienes defects as a foundation for modeling more complex defects that move our model toward that of realistic CF. Using large computational supercells, we can understand how these defects change the electronic structure and vibrational properties of graphene and graphite for interdefect distances near those of the lower experimental limit. The monovacancy opens an electronic bandgap at the K point. Although no such electronic gap is opened by the Dienes defect, both defects introduce flat defect bands near the Fermi energy. The Dienes defect creates long-range deviations of the phonons, leading to substantial broadening of the highest frequency optical modes in the band structure compared to that of the pristine material. In contrast, the phonon changes caused by the monovacancy are short range, and only minor changes in the band structure or phonon density of states were observed. These findings can assist in the interpretation of experimental results by providing atomic-scale insight into key electronic and vibrational features.

Elucidation of the Reaction Mechanism of C2 + N1 Aziridination from Tetracarbene Iron Catalysts.

A combined computational and experimental study was undertaken to elucidate the mechanism of catalytic C2 + N1 aziridination supported by tetracarbene iron complexes. Three specific aspects of the catalytic cycle were addressed. First, how do organic azides react with different iron catalysts and why are alkyl azides ineffective for some catalysts? Computation of the catalytic pathway using density functional theory (DFT) revealed that an alkyl azide needs to overcome a higher activation barrier than an aryl azide to form an iron imide, and the activation barrier with the first-generation catalyst is higher than the activation barrier with the second-generation variant. Second, does the aziridination from the imide complex proceed through an open-chain radical intermediate that can change stereochemistry or, instead, via an azametallacyclobutane intermediate that retains stereochemistry? DFT calculations show that the formation of aziridine proceeds via the open-chain radical intermediate, which qualitatively explains the formation of both aziridine diastereomers as seen in experiments. Third, how can the formation of the side product, a metallotetrazene, be prevented, which would improve the yield of aziridine at lower alkene loading? DFT and experimental results demonstrate that sterically bulky organic azides prohibit formation of the metallotetrazene and, thus, allow lower alkene loading for effective catalysis. These multiple insights of different aspects of the catalytic cycle are critical for developing improved catalysts for C2 + N1 aziridination.