Synthesis, Characterization, and the Platinum-Catalyzed Ring-Opening Polymerization and Stereoselective Dimerization of Silicon-Bridged [1]Ferrocenophanes with Acetylenic Substituents
Bibliographic record
Abstract
Reaction of the lithium acetylides LiC⋮CR (R = Ph, n Bu) with the silicon-bridged [1]ferrocenophane Fe( η -C 5 H 4 ) 2 Si(Me)Cl ( 2a ) at −78 °C was found to result in selective substitution of Cl, forming sila[1]ferrocenophanes with acetylenic substituents Fe( η -C 5 H 4 ) 2 Si(Me)C⋮CR ( 4, R = Ph; 5, R = n Bu). A similar reaction of sila[1]ferrocenophane Fe( η -C 5 H 4 ) 2 SiCl 2 ( 2b ) with 2 equiv of LiC⋮CPh resulted in the substitution of both Cl atoms, forming Fe( η -C 5 H 4 ) 2 Si(C⋮CPh) 2 ( 6 ). Transition metal-catalyzed ring-opening polymerization of monomers 4, 5, and 6 resulted in the formation of high molecular weight ( M n > 10 4 −10 5 ) polyferrocenylsilanes with acetylenic substituents, [Fe( η -C 5 H 4 ) 2 Si(Me)C⋮CR] n ( 7, R = Ph; 8, R = n Bu) and [Fe( η -C 5 H 4 ) 2 Si(C⋮CPh) 2 ] n ( 9 ), respectively. The cyclic dimer [Fe( η -C 5 H 4 ) 2 Si(Me)C⋮CPh] 2 ( 10 ) was isolated from the polymerization mixture derived from 4 . The dimer was shown to exist in the cis configuration by single-crystal X-ray diffraction. Detailed studies on the polymerization of 4 have shown that the ratio of high polymer 7 to cyclic dimer 10 formed in the reaction is highly solvent and concentration dependent. Pyrolysis of polymers 7 and 8 during thermogravimetric analysis (TGA) studies have resulted in the formation of black magnetic ceramics in the highest yields found to date for uncrosslinked polyferrocenylsilane homopolymers (2 h, 900 °C; 7, 81%; 8, 61%).
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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 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| 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) | 0.003 | 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".