Electrochemical and Chemical Reduction of Disulfur Dinitride: Formation of [S<sub>4</sub>N<sub>4</sub>]<sup>−•</sup>, EPR Spectroscopic Characterization of the [S<sub>2</sub>N<sub>2</sub>H]<sup>•</sup> Radical, and X-ray Structure of [Na(15-crown-5)][S<sub>3</sub>N<sub>3</sub>]
Bibliographic record
Abstract
Voltammetric studies of S(2)N(2) employing both cyclic voltammetry (CV) and rotating disk electrode (RDE) methods on GC electrodes at room temperature (RT) revealed two irreversible reduction processes at about -1.4 V and -2.2 V in CH(3)CN, CH(2)Cl(2), and tetrahydrofuran (vs ferrocene) and no observable oxidation processes up to the solvent limit when the scan is initially anodic. However, after cycling the potential through -1.4 V, two new couples appear near -0.3 V and -1.0 V due to [S(3)N(3)](-/0) and [S(4)N(4)](-/0) respectively. The diffusion coefficient D for S(2)N(2) was determined to be 9.13 x 10(-6) cm(2) s(-1) in CH(2)Cl(2) and 7.65 x 10(-6) cm(2) s(-1) in CH(3)CN. Digital modeling of CVs fits well to a mechanism in which [S(2)N(2)](-*) couples rapidly with S(2)N(2) to form [S(4)N(4)](-*), which then decomposes to [S(3)N(3)](-). In situ electron paramagnetic resonance (EPR) spectroelectrochemical studies of S(2)N(2) in both CH(2)Cl(2) and CH(3)CN resulted in the detection of strong EPR signals from [S(4)N(4)](-*) when electrolysis is conducted at -1.4 V; at more negative voltages, spectra from transient adsorbed radicals are observed. In moist solvent or with added HBF(4), a longer-lived spectrum is obtained due to the neutral radical [S(2)N(2)H](*), identified by simulation of the EPR spectrum and density functional theory (DFT) calculations. The chemical reduction of S(2)N(2) with Na[C(10)H(8)] or Na[Ph(2)CO] produces [Na(15-crown-5)][S(3)N(3)], while reduction with cobaltocene gives [Cp(2)Co][S(3)N(3)]. The X-ray structure of the former reveals a strong interaction (Na...N = 2.388(5) A) between the crown ether-encapsulated Na(+) cation and one of the nitrogen atoms of the essentially planar six-membered cyclic anion [S(3)N(3)](-).
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How this classification was reachedexpand
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 | 0.001 | 0.002 |
| Meta-epidemiology (narrow) | 0.003 | 0.003 |
| Meta-epidemiology (broad) | 0.004 | 0.001 |
| Bibliometrics | 0.000 | 0.002 |
| Science and technology studies | 0.001 | 0.002 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.002 | 0.001 |
| Research integrity | 0.004 | 0.003 |
| Insufficient payload (model declined to judge) | 0.000 | 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; both teacher heads agree on what is shown here.
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".