From <em>C</em>-phosphanylated thiazole-2-thiones to phosphaalkenes and tricyclic 1,4-diphosphinines
Bibliographic record
Abstract
The PhD Thesis “From C-phosphanylated thiazole-2-thiones to phosphaalkenes and tricyclic 1,4-diphosphinines” describes investigations on the synthesis of thiazolyl substituted phosphaalkenes, tricyclic 1,4-dihydro-1,4-diphosphinines and 1,4-diphosphinines. The synthesis of the starting material, i.e., (Et2N)2P- and Et2N(Cl)P-substituted thiazole-2-thiones is described in the first part. The latter was converted into a precursor for the synthesis of thiazolyl substituted phosphaalkene and its end-on tungsten(0) complex. Further studies upon deprotonation of the Et2N(Cl)P-substituted thiazole-2-thiones with LDA followed by cyclo-condensation to afford tricyclic 1,4-dihydro-1,4-diphosphinines are described. Furthermore, investigations on the reactivity of the tricyclic 1,4-dihydro-1,4-di-phosphinines towards oxidation, P-functionalization and towards electrophiles were conducted. The reduction of a 1,4-dichloro-1,4-dihydro-1,4-diphosphinine led to the synthesis and isolation of a stable, red-colored 1,4-diphosphinine, which was fully characterized via NMR MS, IR, UV/vis, CV and X-ray diffraction analysis, including also theoretical investigations (L.Nyulaszi). The reactivity of a thiazole-2-thione-derived 1,4-diphosphinine towards dienophiles revealed its dienic nature. Theoretical investigations (L.Nyulaszi) suggested that the LUMO of the 1,4-dphosphinine has larger coefficient at the phosphorus centers, which was experimentally verified using reactions with anionic nucleophiles, and even the very week KHMDS led to anionic phosphanido-related compounds which were isolated and could be quenched with electrophiles. The HOMO is largely concentrated on the thione sulfur centers, which explains why electrophiles such as MeOTf add to the S-centers thus affordinga bis(thiazolium) salt. Finally, first investigations on the reduction of the 1,4-diphosphinine leading to the isolable tricyclic system having two phosphanido-related centers is described.
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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) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.001 | 0.001 |
| Open science | 0.000 | 0.001 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.154 | 0.051 |
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".