Nucleophilic and Electrophilic Molybdenum Terminal Oxo Complexes By Coordination-Induced Bond Weakening of Hydroxo O-H Bonds.
Bibliographic record
Abstract
The extent of coordination-induced bond weakening in aquo and hydroxo ligands bonded to a molybdenum(III) center complexed by a dianionic, pentadentate ligand system was probed by reacting the known complex (B2Pz4Py)Mo(III)-NTf2, I, with degassed water or dry lithium hydroxide. The aquo adduct was not observed, but two LiNTf2 stabilized hydroxo complexes were fully characterized. Computational and experimental work showed that the O-H bond in these complexes were significantly weakened (to ≈ 57 kcal mol-), such that these compounds could be used to form the diamagnetic, d2 neutral molybdenum oxo complex (B2Pz4Py)Mo(IV)O, 2, by hydrogen atom abstraction using the aryl oxyl reagent ArO• (Ar = 2,4,6-tri-tert-butylphenyl). Oxidation of the neutral hydroxo derivative further facilitated production of 2 by significantly enhancing the acidity of the hydroxyl proton. Speciation in these processes was probed by electrochemical and chemical experiments. The terminal oxo complex 2 was smoothly oxidized by one electron to the cationic [(B2Pz4Py)Mo(V)O]+[A]- derivatives [2]+[A]- (A = NTf2 or Al[(OC(CF3)3]4 depending on the oxidizing agent used). Both Mo(IV) and Mo(V)+ oxo complexes were fully characterized and their nucleophilic and electrophilic reaction behavior probed by conducting reactions with the Lewis acid B(C6F5)3 and the Lewis base PPh3. Neutral oxo complex 2 reacts only with the Lewis acid, while the cationic [2]+[A]- reacts only with PPh3, the former by adduct formation, the latter via phosphine oxidation.
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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 | 0.001 | 0.001 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.000 | 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".