Formation of Cyclic Selenium Imides via Acyclic Selenium Imide Chlorides in Cyclocondensation of Selenium Dichloride with <i>tert</i>‐Butylamine
Bibliographic record
Abstract
The energetics and mechanisms of cyclocondensation reactions between SeCl2 and tBuNH2 in 1:3 molar ratio are examined using density functional theory with implicit solvation in tetrahydrofuran at 193 K. The results give strong support for the proposed stepwise pathway consisting of three key steps: 1) formation of an acyclic building block tBuN(H)SeCl, 2) chain growth to ClSe[N(tBu)Se]nCl (n = 1–3, 7–9), and 3) ring closure to 1,3,5‐Se3(NtBu)3 (1), 1,3,5,7‐Se4(NtBu)4 (2), 1,3‐Se3(NtBu)2 (3), or 1,3,5‐Se4(NtBu)3 (4). The paths leading to 3 and 4 include additional redox steps and diradical intermediates to generate SeSe bonds. The proposed paths share common intermediates, which allows the rationalization of the experimental product distribution as well as changes to it upon altering the stoichiometry or the total SeCl2 concentration. The results further show that the successive addition of [N(tBu)Se] units quickly becomes energy neutral, decreasing the likelihood for the formation of molecules with more than eight atoms by cyclocondensation. Plausible mechanisms explaining the formation of the 15‐membered ring 1,3,6,8,11,13‐Se9(NtBu)6 (5) involve the coupling of diradical intermediates or redox processes converting SeCl2 to Se2Cl2, both of which might also play a role in the generation of SeSeSe functionalities in 1,5‐Se6(NtBu)2 (6).
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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) | 0.002 | 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 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".