Studies on the Mechanism of B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>-Catalyzed Hydrosilation of Carbonyl Functions
Bibliographic record
Abstract
The strong organoborane Lewis acid B(C(6)F(5))(3) catalyzes the hydrosilation (using R(3)SiH) of aromatic and aliphatic carbonyl functions at convenient rates with loadings of 1-4%. For aldehydes and ketones, the product silyl ethers are isolated in 75-96% yield; for esters, the aldehydes produced upon workup of the silyl acetal products can be obtained in 45-70% yield. Extensive mechanistic studies point to an unusual silane activation mechanism rather than one involving borane activation of the carbonyl function. Quantitative kinetic studies show that the least basic substrates are hydrosilated at the fastest rates; furthermore, increased concentrations of substrate have an inhibitory effect on the observed reaction rate. Paradoxically, the most basic substrates are reduced selectively, albeit at a slower rate, in competition experiments. The borane thus must dissociate from the carbonyl to activate the silane via hydride abstraction; the incipient silylium species then coordinates the most basic function, which is selectively reduced by [HB(C(6)F(5))(3)](-). In addition to the kinetic data, this mechanistic proposal is supported by a kinetic isotope effect of 1.4(5) for the hydrosilation of acetophenone, the observation that B(C(6)F(5))(3) catalyzes H/D and H/H scrambling in silanes in the absence of substrate, computational investigations, the synthesis of models for proposed intermediates, and other isotope labeling and crossover experiments.
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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) | 0.002 | 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".