H(OEt<sub>2</sub>)<sub>2</sub>[P(1,2‐O<sub>2</sub>C<sub>6</sub>Cl<sub>4</sub>)<sub>3</sub>]: Synthesis, Characterization, and Application as a Single‐Component Initiator for the Carbocationic Polymerization of Olefins
Bibliographic record
Abstract
The development of novel Brønsted acids featuring the hexacoordinate phosphorus(V) anion [TRISPHAT](-) {[1](-)=[P(1,2-O2C6Cl4)3](-)} are reported. The title compound, H(OEt2)2[1], was synthesized from 1,2-(HO)2C6Cl4 (3 equiv) and PCl5 in the presence of diethyl ether. This compound was fully characterized by (1)H, (31)P and (13)C NMR spectroscopy, X-ray crystallography and elemental microanalysis. Dissolution of H(OEt2)2[1] in acetonitrile results in the slow precipitation of crystalline H(OEt2)(NCMe)[1], which was characterized by X-ray diffraction; however, in CD2Cl2 solution the [TRISPHAT](-) anion protonated and ring-opened. The weighable, solid H(OEt2)2[1] was found to be a competent initiator for the polymerization of n-butyl vinyl ether, α-methylstyrene, styrene and isoprene at a variety of temperatures and monomer-to-initiator ratios. At low temperatures, polymers with M(n) >10(5) were obtained for n-butyl vinyl ether and α-methylstyrene whereas slightly lower molecular weights were obtained with styrene and isoprene (10(4) < M(n) <10(5)). The poly(α-methylstyrene) synthesized at -78 °C is syndiotactic-rich (ca. 87% rr) whereas the polystyrene obtained at -50 °C is atactic. The polyisoprene obtained possessed all possible modes of enchainment as well as branched and/or cyclic structures that are often observed in polyisoprene.
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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 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| 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 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".