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 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".