From P‐Functional Thiazol‐2‐thione Derivatives to Phosphaalkenes
Bibliographic record
Abstract
A facile synthetic methodology is reported that permits access to the backbone (Et2N)2P‐substituted thiazol‐2‐thione 2 [(Et2N)2P‐THSMe; THSMe = 3‐methylthiazol‐2‐thione‐5‐yl]. Starting from 2, Et2N(Cl)P‐substituted thiazol‐2‐thione 3 [Et2N(Cl)P‐THSMe] was formed using chloride scrambling with PCl3. Subsequently, nucleophilic substitution using Ph2CHLi afforded [Et2N(Ph2CH)P‐THSMe] (4) which, via reaction with PCl3, afforded [Ph2CHP(Cl)THSMe] (5). Conversion of 4 into phosphaalkene [Ph2C=P‐THSMe] (6) was achieved, but its thermal instability precluded isolation. Complex [κP‐W(CO)5{Ph2CH(Cl)P}‐THSMe] (7) was then synthesized and used to access end‐on complex [W(CO)5(Ph2C=P‐THSMe)] (8); the 1,2‐addition product of 8 with H2O, complex [Ph2CH(OH)P‐THSMe] (10), was confirmed by X‐ray crystallography. The head‐to‐tail dimers of 8, the diastereomeric dinuclear 1,3‐diphosphetane complex 9 were assigned based on NMR results. In contrast, DFT calculations of all regio‐ and stereochemical isomers of 9 revealed a slight energetic preference for the head‐to‐head dimer. However, since transition states could not be localized, a detailed computational rationale for these experimental findings remains open.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| 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 | 0.001 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.003 | 0.001 |
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 source (direct Gemma or distilled Codex), 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".