Preparation of the tricyclo[5.3.1.1<sup>3,9</sup>]dodeca‐1,5‐diyl dication: attempts to prepare a novel µ‐H cation
Bibliographic record
Abstract
Abstract The tricyclo[5.3.1.13,9]dodeca‐3,7‐diyl dication (6) was prepared in situ and characterized by 1H and 13C NMR spectroscopy. Reaction of this dication with isopentane, NaBH4 or H2, in an attempt to prepare the µ‐H cation 7, did result in hydride transfer, but to the ‘outside’ face of the dication, leading to the conventional monocation 8, or rearrangement products of this. This monocation was independently prepared, and is thermally less stable than the dication, rearranging to the 2‐ethyl‐2‐adamantyl cation (19) at −60 °C, ΔG‡ = 16.0 ± 0.6 kcal mol−1. The 2‐methyltricyclo[4.3.1.13,7]undec‐2‐yl cation (20), a likely intermediate in this rearrangement, was also independently prepared and shown to rearrange to 19, ΔG‡ = 14.4 ± 0.3 kcal mol−1, consistent with a stepwise rearrangement process for 8→[20]→19. The structures of dication 6 and monocation 8 were investigated by high‐level ab initio calculations, and modeling studies were carried out to look at the factors that allow dications such as 6 to even be prepared. Copyright © 2001 John Wiley & Sons, Ltd.
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 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) | 0.003 | 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".