Quinoxaline-1,2,3-dithiazolyls Synthesis, EPR characterization, and redox chemistry
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Bibliographic record
Abstract
Oxidation of quinoxalineaminothiol with SCl 2 or S 2 Cl 2 /Cl 2 affords a series of compounds based on the quinoxaline-1,2,3-dithiazole framework QDTA. Under highly oxidizing conditions, the 1,2,3-dithiazolyl ring is opened to afford the acyclic dichlorosulfimino-sulfenyl chlorides Cl x -QDTA-Cl 3 (x = 0, 1, 2). Reduction of these "trichloro" compounds leads to ring closure. For x = 2, reduction using S 2 Cl 2 affords the dithiazolylium chloride [Cl 2 -QDTA][Cl]. For all values of x, reduction with iodide ion (3 mol equiv) affords the corresponding dithiazolyl radical [Cl x -QDTA]. The radicals can be isolated in good yield in crude form, but attempts to purify them by vacuum sublimation lead to thermal degradation. The radicals have nonetheless been fully characterized by EPR spectroscopy, and the assignments of the observed hyperfine coupling constants cross-matched with those obtained by computation at the B3LYP/6-31G** level. The structures of the trichloro compounds Cl x -QDTA-Cl 3 (x = 1, 2) have been confirmed by X-ray crystallography. Crystal data: Cl-QDTA-Cl 3 , monoclinic, space group C2/c, a = 30.561(5) Å, b = 4.9764(9) Å, c = 22.247(4) Å, β = 131.822(14)°, V = 2521.4(8) Å 3 , Z = 8, R(F) = 0.043, and R w (F) [I [Formula: see text] σ (I)] = 0.049; Cl 2 -QDTA-Cl 3 , orthorhombic, space group Pnma, a = 18.627(12) Å, b = 6.848(4) Å, c = 10.926(7) Å, V = 1393.7(15) Å 3 , Z = 4, R(F) = 0.047, and R w (F) [I [Formula: see text] 3σ(I)] = 0.060.Key words: thiazyl radicals, molecular conductors, EPR spectroscopy, quinoxaline, DFT calculations.
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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) | 0.010 | 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