Inside-protonated 1-azaadamantane: computational studies on the structure, stability, and generation
Bibliographic record
Abstract
Post Hartree–Fock and density functional theory methods have been employed to study inside-protonated 1-azaadamantane 7 and its complexes with the fluoride counterion (contact ion pairs) 10 and 11. The study also involved 1-azaadamantane 4, its outside-protonated form 8, and 1-azaadamantane radical cation 17. Inside-protonated 1-azaadamantane 7 is more than 82 kcal mol −1 less stable than out-isomer 8. The repulsive interaction between the internal N + –H group and the azaadamantane cage and a substantial deformation of this cage greatly weaken the C–N and C–C bonds and, consequently, lead to a low kinetic stability of in-ion 7 in the studied unimolecular and bimolecular reactions involving the removal of the encapsulated proton from the cage. Among these reactions, a 7 → 8 rearrangement through a reversible cage opening at the C–N bond was found to be the main transformation channel ([Formula: see text] < 16 kcal mol −1 ) for in-ion 7. This rearrangement can be catalyzed by an external base, e.g., the fluoride anion. A 1,4-hydrogen migration in 1-azaadamantane radical cation 17 as a possible pathway to the inside-protonated 1-azaadamantane 7 was explored. It was found that this process has a prohibitively high activation barrier, [Formula: see text] > 104 kcal mol −1 , and is not able to compete with the α-C–C cleavage of the azaadamantane cage ([Formula: see text] < 26 kcal mol −1 ).
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 | 0.000 | 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 | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.002 | 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".