Terminal Phosphido Complexes of the Ru(η<sup>5</sup>-Cp*) Fragment
Bibliographic record
Abstract
In situ generation of the five-coordinate complex Ru(η 5 -Cp*)(PR 2 )(PPh 3 ) ( 2 ), via dehydrohalogenation of Ru(η 5 -Cp*)Cl(PR 2 H)(PPh 3 ), has allowed its reactivity toward a range of small molecules to be compared with that of its well-studied analogue Ru(η 5 -indenyl)(PR 2 )(PPh 3 ) ( 1 ), in a study designed to assess the likelihood of variable hapticity in the chemistry of complex 1 . Reactions of 2 with hydrogen, carbon monoxide, phenylacetylene, ethylene, acrylonitrile, and 1-hexene demonstrate enhanced nucleophilicity/basicity of the terminal phosphido ligand in 2 relative to that in complex 1 . Complex 2 also exhibits greater lability of the PPh 3 ligand, leading to substitutional product mixtures that were not observed for 1 . Both of these features are consistent with the more electron-rich and sterically imposing nature of the Cp* ligand in 2 relative to the indenyl ligand in 1 . Nevertheless, the fundamental transformations of the phosphido ligand are comparable for the two complexes. This suggests that variable hapticity does not play a role in reactions of indenyl complex 1, since η 5 –η 3 shifts are unlikely to occur for Cp* complex 2 . The implications of these reactivity studies for the design of highly active, yet stable, ruthenium half-sandwich catalysts for hydrophosphination are discussed.
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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 | 0.000 | 0.000 |
| 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".