Exploring the Variable Hapticity of the Arylamide Ligand: Access to σ-Amidophenyl and π-Cyclohexadienylimine Structures
Bibliographic record
Abstract
A study of the preference for σ vs π coordination of the arylamido ligand to a late transition metal shows that LiNPh 2 reacts with RuHCl(PPh 3 ) 3 ( 1 ) to yield the bent-seat piano-stool complex RuH[(η 5 -C 6 H 5 )NPh](PPh 3 ) 2 ( 2a ) but with RuHCl(CO)(PPh 3 ) 3 ( 3 ) to yield the σ-amide RuH(η 1 -NPh 2 )(CO)(PPh 3 ) 2 ( 4 ). The stability of the σ-bound NPh 2 ligand in 4 reflects the π acidity of the CO ligand, which inhibits PPh 3 loss. Carbonylation of 2a at 50 °C affords Ru(CO) 3 (PPh 3 ) 2 ( 8 ) and HNPh 2, suggesting sequential π → σ isomerization and reductive elimination. The phenoxide ligand behaves similarly: RuH(η 5 -C 6 H 5 O)(PPh 3 ) 2 ( 2b ) is formed from 1 but RuH(η 1 -OPh)(CO)(PPh 3 ) 3 ( 5 ) is formed from 3, and carbonylation of 2b gives 8 and phenol, although more forcing conditions are required (90 °C). The crystal structure of 2a is reported.
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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 | 0.001 |
| 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 | 0.001 | 0.001 |
| 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 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".