Divergent Isomerization Behavior and Rhodium(I) Coordination Chemistry of Indenyl Ligands Bearing either One or Two Pnictogen Donor Fragments
Bibliographic record
Abstract
1-(Diphenylphosphino)-2-(dimethylamino)indene ( 2c ) has been prepared in 61% yield and upon exposure to Al 2 O 3 is mostly isomerized to 3-(diphenylphosphino)-2-(dimethylamino)indene ( 2d ) ( 2c: 2d ≈ 1:3); similarly, 1-(diisopropylphosphino)-2-(dimethylamino)indene ( 2a ) is only partially converted to the corresponding C3 isomer ( 2b ) upon treatment with Al 2 O 3 ( 2a: 2b ≈ 3:1). In contrast, 1-(diisopropylphosphino)indene ( 6a ) has been prepared in 92% yield and is easily converted to 3-(diisopropylphosphino)indene ( 6b ) on passing over Al 2 O 3; 0.5 equiv of [(η 4 -COD)RhCl] 2 and 6b combine to give [(κ 1 - P - 6b )(η 4 -COD)RhCl] ( 7 ) in 79% yield. Treatment of either 2-(dimethylamino)indene ( 1 ) or 6b with a stoichiometric amount of n -BuLi, followed by the addition of 0.5 equiv of [(η 4 -COD)RhCl] 2, produces the (η 5 -indenyl)rhodium(I) complexes 8 (53% yield) and 9 (88% yield), respectively, in which the pnictogen donor is apparently not coordinated to the rhodium center. When 2.5 equiv of n -BuLi is combined with 6b and subsequently treated with 0.5 equiv of [(η 4 -COD)RhCl] 2, 9 is also produced, along with a small amount of the unusual Rh 2 Li 2 species 10 . The crystallographically determined structures of 2d, 3 ·C 6 H 6, 7, and 10 ·C 7 H 8 are 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 | 0.000 |
| 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 | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.039 | 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".