Exploring Ligand-Centered Hydride and H-Atom Transfer
Bibliographic record
Abstract
The nickel(II) complex [ON(H)O]Ni(PPh 3 ) ([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(PPh 3 ) afforded the square-planar anion {[ONO cat ]Ni(PPh 3 )} 1–, whereas hydrogen atom transfer from [ON(H)O]Ni(PPh 3 ) to TEMPO • in the presence of added PPh 3 afforded five-coordinate [ONO]Ni(PPh 3 ) 2 that has been structurally characterized. In solution, this five-coordinate complex exists in equilibrium with four-coordinate [ONO]Ni(PPh 3 ), 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(PPh 3 ) in the presence of PPh 3 afforded the octahedral complex, [ONO q ]Ni(OTf)(PPh 3 ) 2, which was characterized as an S = 1, nickel(II) complex. Bond dissociation free energy (BDFE) and hydricity (Δ G ° 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 machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| 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 | 0.001 | 0.001 |
| 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 source (direct Gemma or distilled Codex), 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".