Orthometalation of Tp*Rh(PPh<sub>3</sub>)<sub>2</sub>: Implications for Catalytic Reactivity
Bibliographic record
Abstract
In the course of our studies of the catalytic reactivity of Tp*Rh(PPh 3 ) 2 ( 1 ), we noted considerable decomposition of 1 in reactions conducted in 1,2-dicholoroethane (DCE) requiring extended reaction times (>12 h). Because this decomposition could have significant implications for the catalytic utility of 1, we have undertaken a study of the decomposition process. We herein report that 1 undergoes facile, irreversible orthometalation of a PPh 3 ligand at room temperature in slightly polar solvents, such as THF and 1,2-dichloroethane. In comparison, orthometalation is virtually undetectable in PhCH 3 at room temperature. Fortunately, 1 shows catalytic activity for hydrothiolation and hydrophosphinylation in low-polarity solvents. Accordingly, reactions using 1 (and potentially related complexes) should be conducted in nonpolar solvents or solvent mixtures whenever possible.
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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) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.001 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 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".