Understanding Reactive Sulfur Species Storage from Hybrid S/N Crosstalk Species: Perthionitrite (SSNO<sup>–</sup>) and Thionitrite (SNO<sup>–</sup>) Activation by a Mononuclear Nonheme Fe<sup>II</sup> Complex
Bibliographic record
Abstract
S/N hybrid species, such as perthionitrite (SSNO – ) and thionitrite (SNO – ), play intricate roles in nitric oxide (NO • ) and hydrogen sulfide (H 2 S) biological signaling and transport pathways. Despite this emerging significance, the fundamental reactivities of these species remain largely unexplored. In particular, a significant gap remains in understanding how these S/N hybrid species react with redox active metal centers. Building from this gap, we report here the reactivity of SSNO – and SNO – toward tripodal Fe 2+ complex [Fe( 3 CF 3 -baTren)] − ( 1 ) and examine the associated reactive nitrogen and sulfur species output pathways from these reactions using both spectroscopic and chemical trapping techniques. Specifically, we observe that complex 1 facilitates S–N bond homolysis of SSNO – to give {Fe–NO} 7 complex [Fe( 3 CF 3 -baTren)(NO)] − ( 2 ) and polysulfide radicals, whereas SNO – reacts with 1 to undergo S-centered reduction to give S 2– and NO • . Taken together, these results advance our understanding of how small molecule S/N hybrids react with redox active metal centers and may contribute to metal nitrosyl formation.
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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 | 0.000 | 0.001 |
| Meta-epidemiology (narrow) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.001 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.001 | 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 teacher head, 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".