H<sub>2</sub> Activation by a (PNP)Ir(C<sub>6</sub>H<sub>5</sub>) Complex via the Dearomatization/Aromatization Process of the PNP Ligand: A Computational Study
Bibliographic record
Abstract
Density functional theory calculations have been carried out to explore the mechanism of the H(2) activation by the (PNP)Ir(C(6)H(5)) complex. Our calculations show that the reaction is most likely to go though three steps. The first step (also the rate-determining step) involves the proton transfer from the benzylic position of the PNP ligand to the metal center to form an Ir(III) hydride intermediate, accompanied by the dearomatization of the PNP ligand. Second, H(2) is coordinated to the metal of this Ir(III) intermediate to form a molecular hydrogen complex. Finally, the H-H bond is heterolytically cleaved to produce the final trans-dihydride product, in which the benzylic carbon is protonated, and the PNP ligand is rearomatized. Thus, the H(2) activation by the Ir(I) complex actually involves an Ir(III) hydride complex as a key intermediate. The Ir center and the PNP ligand cooperate in a synergistic manner in the H(2) activation process. The above molecular mechanism could provide reasonable explanations for known experimental facts.
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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) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.001 | 0.000 |
| Scholarly communication | 0.001 | 0.001 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.001 | 0.001 |
| 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 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".