Coordination of a Bifunctional Ligand to a Rhodium(III) Dimethyl Complex: Lewis Acidity Enhancement by Chelation
Bibliographic record
Abstract
The addition of the ambiphilic compound (Me 2 PCH 2 AlMe 2 ) 2 ( 1 ) to Cp*RhMe 2 (DMSO) (DMSO = dimethylsulfoxide) ( 2 ) gives Cp*RhMe 2 (PMe 2 CH 2 AlMe 2 ·DMSO) ( 3 ·DMSO). The addition of Lewis acids (LA) such as La(dbm) 3 (dbm = dibenzoylmethane) and AlMe 3 to a solution of complex 3 ·DMSO gives a competition reaction that results in the formation of LA·DMSO and Cp*RhMe 2 (PMe 2 CH 2 AlMe 2 ) ( 3 ). When heated to 40 °C, complex 3 ionizes to a putative zwitterionic species, Cp*Rh + Me(PMe 2 CH 2 AlMe 3 - ) ( 3 ‘), which is converted to [Cp*Rh(Me)(μ 2 -η 2 -Me 2 PCH 2 )] 2 ( 4 ) irreversibly. Spin saturation transfer experiments demonstrated that the rate of the methyl abstraction by the alane moiety was 0.76 ± 0.09 s - 1, while the rate of abstraction of the methyl in Cp*RhMe 2 (PMe 3 ) by AlMe 3 was 0.10 ± 0.02 s - 1 . The zwitterionic species 3 ‘ could be trapped in solution by addition of PMe 3 to afford both Cp*Rh + Me(PMe 3 )(Me 2 PCH 2 AlMe 3 - ) ( 5 ) and [Cp*Rh + Me(PMe 3 )(Me 2 PCH 2 AlMe 2 )]AlMe 4 - ( 6 ). When compound 1 was added to complex 3 ‘, the formation of the zwitterionic complex Cp*Rh + Me(η 2 -Me 2 PCH 2 Al - Me 2 CH 2 PMe 2 ) ( 7 ) was observed.
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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 | 0.001 | 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 | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.029 | 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".