On The Lower Lewis Basicity of Siloxanes Compared to Ethers
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Bibliographic record
Abstract
Abstract 1,3‐Dimethyldisiloxane, O(SiH 2 Me) 2 , diethyl ether, OEt 2 , and their metal complexes (Li + ,Ag + ) have been used as model systems to uncover the reasons underlying the lower Lewis basicity of siloxanes compared to analogous ethers. Bonding in the metal complexes has been analyzed with quantum theory of atoms in molecules as well as natural bond orbital theory. The binding to Li + by O(SiH 2 Me) 2 and OEt 2 is largely of monopole – dipole type whereas binding of Ag + also shows small charge transfer components. The more ionic Si–O bonds in O(SiH 2 Me) 2 compared to C–O bonds in OEt 2 lead to more negative charge on the oxygen atom of O(SiH 2 Me) 2 but the electrostatic attraction between metal cations and OEt 2 is calculated to be slightly stronger by interacting quantum atoms energy decomposition analysis. The lower electrostatic attraction by O(SiH 2 Me) 2 is due to repulsion between positively charged silicon atoms and the metal cations that compensate for the stronger attraction from the oxygen atom relative to OEt 2 . The total interaction of metal cations with O(SiH 2 Me) 2 was calculated to be almost as strong as that with OEt 2 and the lower stability of O(SiH 2 Me) 2 complexes and the lower Lewis basicity of O(SiH 2 Me) 2 is attributed to changes in the bonding and polarization of the ligands in the presence of metal cations. The polarization of O–Si bonds in O(SiH 2 Me) 2 raises the energy of the molecule more than does the polarization O–C bonds in OEt 2 . Despite the lower stability of O(SiH 2 Me) 2 metal complexes, solid state reaction enthalpies arising from a volume‐based thermodynamics approach suggest that they could be stabilized with a sufficiently large anion such as [Al(OR F ) 4 ] – .
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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 | 0.001 |
| 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 | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.004 | 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 it