Substrate‐Mediated Deactivation of a Ru(P<i><sup>t</sup></i><sup>Bu</sup><sub>2</sub>N<sup>Bn</sup><sub>2</sub>) Cooperative Complex
Bibliographic record
Abstract
Abstract Ligand design for metal–ligand cooperative (MLC) catalysis is inherently more complex than that for traditional non‐cooperative ligands. The basicity, sterics and structure of the acid/base group in MLC proton‐transfer (PT) complexes, for instance, undoubtedly influence catalyst performance. Herein, we evaluate the highly tunable P R 2 N R′ 2 (1,5‐R′‐3,7‐R‐1,5‐diaza‐3,7‐diphosphacyclooctane) ligand family for the first time in an organic transformation. With [Ru(Cp)(P t Bu 2 N Bn 2 )(MeCN)][PF 6 ] as the catalyst, no turnover was observed in the anti‐Markovnikov hydration of alkynes, a known PT MLC reaction. Treatment of the cooperative complex with phenylacetylene affords a vinylammonium product in which the pendant nitrogen atom of the P t Bu 2 N Bn 2 ligand forms a Lewis acid–base adduct with the alpha‐carbon atom of the vinylidene intermediate. Characterization by X‐ray crystallography and NMR spectroscopy conclusively assign this structure in both the solid and the solution state. The adduct formation is irreversible, and the adduct is characterized as a catalyst deactivation product.
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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 | 0.002 | 0.003 |
| Meta-epidemiology (narrow) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.002 | 0.001 |
| Bibliometrics | 0.000 | 0.002 |
| Science and technology studies | 0.000 | 0.001 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.002 | 0.000 |
| Research integrity | 0.000 | 0.002 |
| Insufficient payload (model declined to judge) | 0.001 | 0.001 |
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".