Subtle Interactions and Electron Transfer between U<sup>III</sup>, Np<sup>III</sup>, or Pu<sup>III</sup> and Uranyl Mediated by the Oxo Group
Bibliographic record
Abstract
Abstract A dramatic difference in the ability of the reducing An III center in AnCp 3 (An=U, Np, Pu; Cp=C 5 H 5 ) to oxo‐bind and reduce the uranyl(VI) dication in the complex [(UO 2 )(THF)(H 2 L)] (L=“Pacman” Schiff‐base polypyrrolic macrocycle), is found and explained. These are the first selective functionalizations of the uranyl oxo by another actinide cation. At‐first contradictory electronic structural data are explained by combining theory and experiment. Complete one‐electron transfer from Cp 3 U forms the U IV ‐uranyl(V) compound that behaves as a U V ‐localized single molecule magnet below 4 K. The extent of reduction by the Cp 3 Np group upon oxo‐coordination is much less, with a Np III ‐uranyl(VI) dative bond assigned. Solution NMR and NIR spectroscopy suggest Np IV U V but single‐crystal X‐ray diffraction and SQUID magnetometry suggest a Np III ‐U VI assignment. DFT‐calculated Hirshfeld charge and spin density analyses suggest half an electron has transferred, and these explain the strongly shifted NMR spectra by spin density contributions at the hydrogen nuclei. The Pu III –U VI interaction is too weak to be observed in THF solvent, in agreement with calculated predictions.
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How this classification was reachedexpand
Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.001 | 0.000 |
| Meta-epidemiology (narrow) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.002 | 0.000 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one teacher head, not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".