Dehydrogenative Oligomerization of PhSiH<sub>3</sub> Catalyzed by (1-Me-Indenyl)Ni(PR<sub>3</sub>)(Me)
Bibliographic record
Abstract
The complexes (1-Me-Ind)Ni(PR 3 )Me (Ind = indenyl; R = Ph, 1; Cy, 2; Me, 3 ) can act as single-component precatalysts for the dehydrogenative oligomerization of PhSiH 3 to (PhSiH) n with M w up to 1.6 × 10 3 in the case of 3 . The catalytic Si−Si bond formation is initiated by a second-order, concerted reaction between the Ni-Me precursor and PhSiH 3 which releases CH 4 . Kinetic studies of this Si−H bond activation step gave the following activation parameters for the reaction of 3 with PhSiH 3: Δ H ⧧ = 10.7 ± 0.7 kcal·mol - 1; Δ S ⧧ = −42 ± 2 eu; k H / k D (for reaction with PhSiD 3 at 313 K) = 9.8 ± 0.5. The Ni-SiPhH 2 species presumed to form in this reaction was not detected directly, but the presence of 1-SiPhH 2 -3-Me-Ind in the reaction mixtures, coupled with the fact that Ni(PMe 3 ) 4 is an active precatalyst for the oligomerization of PhSiH 3, suggests that the silyl intermediate undergoes a reductive elimination to generate Ni(0) species which might be involved in the catalysis.
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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 | 0.001 |
| Bibliometrics | 0.000 | 0.002 |
| 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) | 0.006 | 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; 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".