Bis(acyl)phosphide Complexes of U(III)/U(IV): A Case of a Hidden Redox-Active Ligand
Bibliographic record
Abstract
The recently reported tris(bis(2,4,6-triisopropylbenzoyl)-phosphide)uranium (U III ( tripp BAP) 3, 2 ) complex ( Inorg. Chem . 2022, 61 (32), 12508–12517) demonstrated a silent 31 P NMR spectrum. This complex was described as a U(III) complex with an organic radical ligand fragment. Moreover, the EPR spectrum of 2 was indicative of an organic radical in the ligand framework complexed to uranium, in contrast to that of U IV ( mes BAP) 4, 1 . Herein, with the help of relativistic density functional theory (DFT) calculations, the electronic structures of 1, 2, and U( mes BAP) 3 ( 4 ) are examined in an effort to understand the unusual 31 P NMR spectrum of 2 . Results indicate the reduction of the carbonyl bonds and delocalization of the electrons over the ligands, indicative of U → L backbonding. Additionally, the reduced acyl carbons are found to exist as ketyl radicals [O═C • – ] that are responsible for the silent 31 P NMR spectra of 2 . These findings demonstrate the redox noninnocent nature of BAP – in 2 and 4, causing uranium to exist in a formal oxidation state of +4.
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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 | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.004 | 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".