A [CoSiH<sub>2</sub>] Silylene Synthon Provides Modular Access to Homo- and Heterobimetallic [Co═Si═M] (M = Co, Fe) Silicide Complexes
Bibliographic record
Abstract
High Resolution Image Download MS PowerPoint Slide Base-stabilized [BP 3 i Pr ](H) 2 CoSiH 2 (DMAP) ( 1, [BP 3 i Pr ] = PhB(CH 2 P i Pr 2 ) 3 –; DMAP = 4-dimethylaminopyridine) is a rare instance of a synthon for the simplest “parent” silylene complex (LM═SiH 2 ). Complex 1 was accessed in high yields via double Si–H bond activation in SiH 4 by [BP 3 i Pr ]Co(DMAP), and in solution, it undergoes rapid exchange between bound and free DMAP by an associative mechanism (as determined by variable-temperature 1 H NMR dynamic studies). The DMAP ligand of 1 is readily displaced by metal-based fragments that bind silicon and cleave the Si–H bonds of the SiH 2 moiety to produce bimetallic [Co═Si═M] (M = Co, Fe) molecular silicides. Thus, treatment of 1 with 0.5 equiv of (LCo I ) 2 (μ-N 2 ) (L = a tripodal ligand) resulted in the spontaneous formation of [BP 3 i Pr ](H) 2 Co═Si═Co(H) 2 L (L = [BP 2 t Bu Pz], PhB(CH 2 P t Bu 2 ) 2 (pyrazolyl) − ( 3 ); Tp″, HB(3,5-diisopropylpyrazolyl) 3 – ( 4 )) with the concomitant release of DMAP. The symmetrical silicide [BP 3 i Pr ](H) 2 Co═Si═Co(H) 2 [BP 3 i Pr ] ( 5 ) was prepared by treatment of a mixture of 1 and [BP 3 i Pr ]Co(DMAP) with 2 equiv of Ph 3 B, which in this case is required to sequester DMAP as the elimination product Ph 3 B-DMAP. A heterobimetallic silicide, [BP 3 i Pr ](H) 2 Co═Si═Fe(H) 2 [SiP 3 i Pr ] ( 7; [SiP 3 i Pr ] = PhSi(CH 2 P i Pr 2 ) 3 ), was obtained via in situ KC 8 reduction of [SiP 3 i Pr ]FeCl and subsequent addition of 1 and Ph 3 B. These transformations involving a metal–SiH 2 derivative demonstrate a fundamentally new type of reactivity for silylene complexes and provide a unique synthetic method for construction of molecular silicide complexes.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
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 | 0.001 |
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 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".