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 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) | 0.001 | 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".