On the Interaction of Phosphines with High Surface Area Mesoporous Silica
Bibliographic record
Abstract
To increase the efficiency and selectivity of homogeneous catalysts, particularly useful in the synthesis of fine chemicals and drugs, fine-tuning of the steric and electronic properties of the complexes can be achieved by modification of the ligands in the coordination sphere of the metal center. Considerable efforts have been devoted in order to immobilize such well-defined catalysts on solid substrates, e.g., silica, to facilitate catalysts’ recovery and to reduce contamination of desired products by metallic impurities. However, the presence of the silica surface can play a very important role in tuning the electronic properties of the metal, its steric environment, or in participating in the reactivity of the complex. In this context, several moieties have been used to anchor metallic catalysts on surfaces, but one of the most interesting is phosphine. Herein, we report on the addition of PPh 2 Cl to mesoporous silica, which leads to the grafting and the oxidation of the phosphine species, even in the absence of oxygen, and that the nature of the surface plays an important role in secondary interactions, e.g., hydrogen bonding, and modifies the spectroscopic properties of the functional groups on the surface. In particular, the chemical shift of the phosphorus resonance in the 31 P NMR spectra is altered by hydrogen bonding between available silanol or water molecules present on the silica surface and the phosphorus oxide. The DFT models developed for this process are in direct accordance with the experimental results and demonstrate firmly that the oxidation of the phosphine after grafting of ClPR 2 is highly favored thermodynamically and occurs with the formation of Si–Cl bonds on the surface. Passivation of the surface with hexamethyldisilazane limits the extent of the H-bonding between the surface and the oxide and also leads to some substitution reaction between bound phosphorus species and the trimethylsilyl (TMS) moieties. These findings offer new knowledge critical to fully ascertain the environment and the stability of immobilized phosphine-containing catalytic systems and thus further broaden the range of their reactivity.
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 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 | 0.001 | 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) | 0.001 | 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".