Indenyl Hemilability: Unveiling a Masked (η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Ru(κ<sup>2</sup>-<i>P</i>,<i>C</i>arbene) Zwitterion Via Facile and Reversible Ru−C(sp<sup>3</sup>) Bond Cleavage
Bibliographic record
Abstract
Data obtained from dynamic NMR investigations and reactivity studies revealed that the isolable, 18-electron Cp*Ru(κ 3 - P, C, C′ ) complex 3 provides access to the reactive, coordinatively unsaturated Cp*Ru(κ 2 - P, C ) zwitterionic intermediate 4 by way of an unprecedented and reversible Ru−C(sp 3 ) bond cleavage process that can be described as ‘indenyl hemilability’. Indirect support for the reversible generation of 4 from 3 was obtained through the isolation of adducts of the type 4·L upon treatment of 3 with various L-donor substrates (L = CO, PPh 3, PHPh 2, 4-dimethylaminopyridine, NH 3, piperidine, and 2,6-dimethylaniline). The reactivity observed upon treatment of 3 with E−H containing substrates (H 2, i PrOH, Ph 3 SiH, Ph 2 SiH 2, PhNH 2, and pyrrole) can be rationalized in terms of net cooperative substrate activation involving the Lewis acidic metal fragment and the Lewis basic indenide unit in the reactive intermediate 4 . In the apparent reaction of 4 with PHPh 2 and PH 2 Ph, an unusual ancillary ligand rearrangement involving the net metathesis of P−H and C−N bonds was observed, resulting in the formation of zwitterionic Cp*Ru(=CH(NHMe))(κ 2 - P, P ) complexes that feature the first examples of κ 2 - P, P -indenide ligation.
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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 | 0.002 | 0.001 |
| Meta-epidemiology (narrow) | 0.003 | 0.003 |
| Meta-epidemiology (broad) | 0.003 | 0.002 |
| Bibliometrics | 0.001 | 0.003 |
| Science and technology studies | 0.002 | 0.001 |
| Scholarly communication | 0.001 | 0.002 |
| Open science | 0.002 | 0.002 |
| Research integrity | 0.002 | 0.002 |
| Insufficient payload (model declined to judge) | 0.005 | 0.001 |
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; both teacher heads agree on what is shown here.
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".