Mechanistic Insights into the Coupling of Hydrosilanes and Alcohol-Amines for Hydrogen Production
Bibliographic record
Abstract
High Resolution Image Download MS PowerPoint Slide The production of hydrogen on-demand via the dehydrogenative coupling of hydrosilanes and alcohol-amines, conducted at room temperature without solvents nor catalysts, marks a significant advancement in the pursuit of greener energy sources. This work deals with the reaction mechanism of the dehydrogenative coupling of phenyl silane (PhS) and 2-(methylamino)-ethanol (MEA) as well as the interference of hydrolysis/condensation and disproportionation reactions when alkoxy-containing hydrosilanes, such as triethoxysilane (TES), are used. DFT methods were used to calculate the thermodynamic properties of the reactions involved (Δ r G °, Δ r H °, and Δ r S °), the hydride donating ability of the reactants and intermediate products (HDA) as well as the Mulliken charges. These theoretical data complemented NMR and GC experiments to identify the most likely reaction pathway. Our results suggest the occurrence of multiple reaction pathways involving the nucleophilic attack of OH groups, and to a lesser extent NH groups, on the Si–H bond, leading to the formation of Si–O and Si–N containing products and the release of hydrogen. However, due to the low stability and high entropic contribution in the formation of Si–N containing products compared to their Si–O containing counterparts, their formation seems unfavorable, and no products containing only Si–N bonds were detected. However, the product with mixed Si–N and Si–O bonding, PhSiH(O−)(N−), was detected as a minor product. The high hydride donating ability of Si–O containing products led to such species undergoing consecutive nucleophilic attacks on their Si–H bonds by the hydroxyl group in MEA until complete dehydrogenation, ultimately leading to the formation of PhSi(O−) 3 as the main reaction product.
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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) | 0.000 | 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) | 0.000 | 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 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".