[1]Metallocenophanes (M = Fe, Ru) of Heavier Group 13 Elements (E = Al, Ga): Synthesis, Characterization, and Ring-Opening Polymerization
Bibliographic record
Abstract
Two new [1]ruthenocenophanes, Ru(η 5 -C 5 H 4 ) 2 E(Me 2 Ntsi) (Me 2 Ntsi = C(SiMe 3 ) 2 SiMe 2 NMe 2; E = Al, Ga), bridged by aluminum ( 3a ) and gallium ( 3b ), were synthesized by reaction of dilithioruthenocene with (Me 2 Ntsi)ECl 2 in good to moderate yields ( 3a, 80%; 3b, 36%). Both species were analyzed by standard techniques (multinuclear NMR spectroscopy, elemental analysis, UV−vis, MS), and their molecular structures were deduced from single-crystal X-ray analysis. Compared to the analogous [1]ferrocenophanes 2a,b, compounds 3a,b showed an increased ring tilt as indicated by the tilt angle α ( 2a, α = 14.33(14)°; 3a, α = 20.31(19)°; 2b, α = 15.83(19)°; 3b, α = 20.91(19)°). Ring-opening polymerization (ROP) with previously published aluminum- and gallium-bridged [1]ferrocenophanes Fe(η 5 -C 5 H 4 ) 2 E(Pytsi) (Pytsi = C(SiMe 3 ) 2 SiMe 2 (2-C 6 H 4 N); E = Al ( 1a ), Ga ( 1b )) and Fe(η 5 -C 5 H 4 ) 2 E(Me 2 Ntsi) (E = Al ( 2a ), Ga ( 2b )) and the [1]ruthenocenophanes 3a,b (this paper) has been shown to be very sluggish or unsuccessful. Only the ROP of 1b with [Pd(dba) 2 ] (2 mol %, toluene, 25 °C, 48 h) resulted in polymeric material (GPC analysis: M w = 2.11 × 10 4, PDI = 3.0).
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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 | 0.000 |
| 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) | 0.015 | 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".