Synthesis and structures of 1,3-bis(organochalcogenyl) distannatrisilabicyclo[1.1.1]pentanes
Bibliographic record
Abstract
The heteronuclear [1.1.1]propellane Sn2Si3Mes6 (1; Mes = 2,4,6-Me3C6H2) was reacted with the dichalcogenyl compounds PhE–EPh (E = S, Se, or Te) to furnish the 1,3-bis(organochalcogenyl) distannatrisilabicyclo[1.1.1]pentanes 3 (E = S), 4 (E = Se), and 5 (E = Te). The E–E bond addition reaction is reminiscent of the formation of FcS–Sn(SiMes2)3Sn–SFc (2; Fc = ferrocenyl) reported previously. Contrary to 2, for which it was shown that its formation can be enhanced by daylight, the analogous clusters 3–5 are very sensitive to light in solution. Solid samples are, however, stable for a prolonged period of time. All three compounds were characterized in detail, including X-ray structure analyses on single crystals of 3 and 5. The core structure connectivities of the clusters were fully confirmed by 119Sn, 77Se, and 125Te NMR spectroscopy, among others. In particular, the 117Sn–119Sn coupling constant between the formally nonbonded bridgehead tin atoms nicely correlates with the interbridgehead distance, i.e., a larger distance is associated with a smaller 117Sn–119Sn coupling constant, and vice versa. This coupling is mediated by so-called “back-lobe-to-back-lobe” interactions through cage. The detection of two different 77Se–119Sn and 125Te–119Sn couplings each (i.e., 1J and 2J) further supported these findings.
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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) | 0.002 | 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".