New Racemic Planar-Chiral Metalloligands Derived from Donor-Substituted Indenes: A Synthetic, Structural, and Catalytic Investigation
Bibliographic record
Abstract
The synthesis and characterization of a new family of (η 5 -indenyl)ML n complexes (ML n = Mn(CO) 3, Cp*Ru, or Cp*Fe; Cp* = η 5 -C 5 Me 5 ) derived from 3-P i Pr 2 -indene, 1-P i Pr 2 -2-NMe 2 -indene ( 1a[H] ), or 1-P(S) i Pr 2 -2-NMe 2 -indene ( 1b[H] ) are described. Lithiation of 1b[H] followed by treatment with BrMn(CO) 5, 0.25 equiv of [Cp*RuCl] 4, or Cp*Li/FeCl 2 provided the corresponding (η 5 - 1b )ML n complexes (ML n = Mn(CO) 3, 2a, 96%; Cp*Ru, 2b, 87%; or Cp*Fe, 2c, 55%). Similarly, treatment of 1a[Li] with 0.25 equiv of [Cp*RuCl] 4 or Cp*Li/FeCl 2 provided the corresponding (η 5 - 1a )ML n complexes (ML n = Cp*Ru, 3b, 74%; or Cp*Fe, 3c, 62%). Whereas combination of 3b and 0.5 equiv of [(COD)RhCl] 2 afforded [(COD)Rh(κ 2 - P, N - 3b )] + Cl - ( [4b] + Cl -; 49% isolated yield), under similar conditions 3c was observed to undergo a decomposition reaction resulting in the formation of the zwitterionic complex (COD)Rh(κ 2 - P, N - 1a ) ( 5; COD = η 4 -1,5-cyclooctadiene). Each of 3a − c was observed to react cleanly with [(COD)Rh(THF) 2 ] + BF 4 - (prepared in situ) to give the corresponding [(COD)Rh(κ 2 - P, N - 3a − c )] + BF 4 - complex ( [4a − c] + BF 4 -; 87%, 96%, and 89% isolated yield, respectively). Whereas lithiation of 3-P i Pr 2 -indene followed by the addition of BrMn(CO) 5 generated a complex mixture of products, similar reactions employing 0.25 equiv of [Cp*RuCl] 4 or Cp*Li/FeCl 2 afforded 6b or 6c in 98% and 43% yield, respectively. Treatment of 6b with 0.5 equiv of [(COD)RhCl] 2 allowed for the isolation of (COD)RhCl(κ 1 - P - 6b ) 7 in 96% isolated yield. Each of [4a − c] + BF 4 - proved to be an active catalyst for addition of pinacolborane to styrene, with the observed regioselectivity being dependent on the nature of the η 5 -coordinated metal fragment, as well as the solvent employed. Single-crystal X-ray diffraction data for 2a, 2b, 2c, 3b, [4c] + BF 4 -, and 7 are provided.
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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) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.001 |
| 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".