Exploring Ligand-Centered Hydride and H-Atom Transfer
Bibliographic record
Abstract
The nickel(II) complex [ON(H)O]Ni(PPh3) ([ON(H)O]2– = bis(3,5-di-tert-butyl-2-phenoxy)amine), bearing a protonated redox-active ligand, was examined for its ability to serve as a hydrogen atom (H•) and hydride (H–) donor. Deprotonation of [ON(H)O]Ni(PPh3) afforded the square-planar anion {[ONOcat]Ni(PPh3)}1–, whereas hydrogen atom transfer from [ON(H)O]Ni(PPh3) to TEMPO• in the presence of added PPh3 afforded five-coordinate [ONO]Ni(PPh3)2 that has been structurally characterized. In solution, this five-coordinate complex exists in equilibrium with four-coordinate [ONO]Ni(PPh3), and this ligand exchange equilibrium correlates with a valence tautomerization between the redox-active ligand and the nickel center. Abstraction of a hydride from [ON(H)O]Ni(PPh3) in the presence of PPh3 afforded the octahedral complex, [ONOq]Ni(OTf)(PPh3)2, which was characterized as an S = 1, nickel(II) complex. Bond dissociation free energy (BDFE) and hydricity (ΔG°H–) measurements benchmark the thermodynamic propensity of this complex to participate in ligand-centered H• and H– transfer reactions.
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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) | 0.000 | 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 | 0.000 |
| Insufficient payload (model declined to judge) | 0.005 | 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".