Heavy Atom Analogues of 1,2,3-Dithiazolylium Salts: Preparation, Structures and Redox Chemistry
Bibliographic record
Abstract
Synthetic routes to salts of the benzo[1,2,3]thiatellurazolylium cation [2c](+) and its selenium analogue [2b](+) are described. Access to the cation frameworks involves the intermediacy of N,N,S-trisilylated 2-aminobenzenethiol. The latter reacts smoothly with selenium and tellurium halides ECl4 (E = Se, Te) to afford the desired heterocyclic benzo cations [2b](+) and [2c](+) as their chloride salts. Anion exchange provides the corresponding GaCl4(-), OTf(-) and TeCl5(-) salts of [2c](+), all of which have been characterized by X-ray crystallography. While the gallate salts of the sulfur and selenium cations [2a](+) and [2b](+) crystallize as ion-paired cations and anions, salts of [2c](+) adopt solid-state structures that display strong association of the cations via short intermolecular Te-N' bonds. However, crystallization of [2c](+) salts in dichloroethane in the presence of GaCl3 leads to cleavage of the dimers and the formation of a Lewis acid adduct at nitrogen. Reduction of the benzo cations [2a,b](+) affords the respective radicals 2a,b, both of which have been characterized by electron paramagnetic resonance (EPR) spectroscopy. Attempts to generate the corresponding radical 2c have been unsuccessful, although a material of nominally correct elemental composition can be generated by chemical reduction. The energetics of association of [2a,b,c](+) in solution has been probed by means of density functional theory calculations using the polarized continuum model. The results suggest that the dimeric nature of the Te-centered cation is retained in solution. The strength of the interaction is, however, less than in N-alkylated tellurodiazolylium salts.
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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 | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.002 | 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".