Synthesis, Electronic Structures, and Electrochemistry of 3‐Triarylphosphoraniminato‐1,3,5‐trithia‐2,4,6,8‐tetrazocines: Detection of Trithiatetrazocinyl Radical Anions
Bibliographic record
Abstract
Abstract Reaction of the bicyclic sulfur‐nitrogen heterocycles RC 6 H 4 CN 5 S 3 (R=4‐CH 3 O, 4‐CH 3 , 4‐H, 4‐Cl, 4‐CF 3 , 3‐CF 3 ) with PR’ 3 (R′=C 6 H 5 or 4‐CH 3 OC 6 H 4 ) produces 3‐phosphoraniminato‐7‐aryl‐1,3,5‐trithia‐2,4,6,8‐tetrazocines RC 6 H 4 CN 4 S 3 NPR’ 3 . In all cases, only the endo ‐isomers were isolated and characterized by 1 H, 31 P, and 19 F NMR as well as UV spectroscopy and X‐ray crystallography. RB3LYP/6‐311+G(d,p)// RB3LYP/6‐31G(d,p) computations were undertaken to help explain the atom‐exact syntheses via intermediates previously detected spectroscopically. Three reasonable intermediates have been computed as stationary points with energies consistent with the observed reaction path. Cyclic and square‐wave voltammetry studies of RC 6 H 4 CN 4 S 3 NPR’ 3 , using a glassy carbon working electrode in CH 2 Cl 2 with 0.4 M [ n Bu 4 N][PF 6 ], reveal two IRR reduction processes at RT in all cases at approximately −1.9 and −2.2 V, respectively, and one IRR oxidation process at approximately +1.0 V (versus Fc +/0 ). [RC 6 H 4 CN 4 S 3 NPR’ 3 ] −. radical anions (R’=4‐CH 3 OC 6 H 4 , R=4‐CH 3 O, 4‐H, 4‐CF 3 ) were detected at −50 °C in CH 2 Cl 2 by using in situ electrolysis and simultaneous electron paramagnetic resonance spectroscopy: [4‐RC 6 H 4 CN 4 S 3 NP(4‐CH 3 OC 6 H 4 ) 3 ] −. , estimated a ( 31 P)=0.078 mT, a ( 14 N 1 )=0.031 mT, a ( 14 N 2,3 )=0.256 mT, a ( 14 N 4,5 )=0.341 mT. The signals decay rapidly, but after the electrolysis is ended, a persistent EPR signal is always obtained with EPR parameters that match known 4‐aryl‐1,2,3,5‐dithiadiazolyls, that is, a (N)=0.51 mT and g =2.0105, which are consistent with the production of [4‐CF 3 ‐C 6 H 4 CN 2 S 2 ] . .
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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) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| 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; 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".