Coordination of Ethylene to a Zwitterionic Rh(III) Half-Sandwich Complex: Influence of Ambiphilic Ligands on Reactivity
Bibliographic record
Abstract
The reactivity of Rh(III) half-sandwich complex Cp*RhMe 2 (κ P -μ Al-Me PMe 2 CH 2 AlMe 2 ) 2 (Cp* = η 5 -pentamethylcyclopentadienyl) with ethylene was investigated. Coordination of ethylene (or ethylene- d 4 ) gave a mixture of products including as principal species zwitterionic complexes Cp*Rh + Me(C 2 H 4 )(PMe 2 CH 2 AlMe 3 − ) 4 (or 4 - d 4 ) and [Cp*Rh + Me(C 2 H 4 )(PMe 2 CH 2 AlMe 3 − )][AlMe 3 ] ( 4′ ), after the abstraction of a Rh-methyl group by the pendant Lewis acid, and Cp*RhMe 2 (PMe 2 CH 2 AlMe 2 ·C 2 H 4 ) ( 5 ). Heating this reaction mixture at 50 °C results in the generation of propene (or propene- d 3,4 ), methane (or methane- d 1 ), and trace amounts of butene, as organic materials, as well as previously characterized [Cp*RhMe(μ 2 -η 2 (P,C)-PMe 2 CH 2 )] 2 ( 10 ) and rhodium(I) species. Two different pathways for the reactivity of the zwitterionic π-complex were investigated by density functional theory (DFT). It is likely that propene is formed by β-hydride elimination from a cationic Rh-propyl fragment that is generated either by insertion of ethylene into a Rh−C bond or by a nucleophilic attack of the methyl-aluminate fragment on coordinated ethylene. After release of propene, the neutral complex Cp*RhHMe(PMe 2 CH 2 AlMe 2 ) 11 is most likely responsible for the reductive elimination of methane.
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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) | 0.001 | 0.000 |
| 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) | 0.010 | 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".