Ru‐Catalyzed Alkene Hydrophosphination: Correlating Substrate Scope with An Outer‐Sphere Mechanism
Bibliographic record
Abstract
Abstract A detailed examination of substrate scope is described for alkene hydrophosphination catalyzed by a series of Cp*Ru complexes. An outer‐sphere mechanism is proposed that involves nucleophilic addition of a Ru phosphido ligand to the alkene and subsequent proton transfer to the resulting phospha‐carbanion from Ru‐bound substrate phosphine. Selected kinetic studies and the observation of catalyst resting state complexes that inevitably contain both a reactive phosphido ligand and substrate phosphine suggest that the conjugate addition is turnover limiting. However, analysis of catalyst activities as a function of the alkene activating group, and observation of off‐cycle alkene oligomerization initiated by the phospha‐carbanion intermediate for some alkene and phosphine substrates point to a more complex situation. These results suggest that alkenes that are “too” activated or substrate phosphines that are not sufficiently P─H acidic cause the intramolecular proton transfer to become turnover‐limiting, with rates sensitive to the conjugate addition “pre‐equilibrium”. This unusual compilation of experimental evidence for the impact of substrate variation on the activity and selectivity of a hydrophosphination catalyst provides insights for guiding future catalyst (re)design, including the challenge of providing a coordination environment that enhances phosphine P─H acidity to achieve a broader substrate phosphine scope.
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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 | 0.001 |
| 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) | 0.001 | 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".