Heavy Atom Analogues of 1,2,3-Dithiazolylium Salts: Preparation, Structures and Redox Chemistry
Why this work is in the frame
A frame that forgets how it found something cannot be audited. These are the routes that admitted this work.
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.
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.
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 | 0.000 |
| 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) | 0.004 | 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