Synthesis and Properties of Hypercoordinate Stannanes and Polystannanes
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Bibliographic record
Abstract
<p>Asymmetric tetraorganotin (IV) compounds containing either a flexible propyl alcohol ligand (<strong>10</strong>) or a semi-flexible ethyl 2-pyridyl ligand <strong>(11</strong>) were synthesized in good yields via select hydrostannylation reactions. The triphenyl derivatives were converted in good yields to their dihalide stannane intermediates (<strong>6</strong>, <strong>7</strong>), respectively, by mild sequential chlorination with HCl or by reaction with Br<sub>2</sub>. The dihalides were converted to reactive dihydride monomers (<strong>8</strong>, <strong>9</strong>) by a reaction with LiAlH<sub>4</sub> or NaBH<sub>4</sub> in good yields. All stannane intermediates and monomers were fully characterized by NMR (<sup>1</sup>H, <sup>13</sup>C, <sup>119</sup>Sn) spectroscopy and high-resolution mass spectrometry. DFT calculations were also performed on the ethyl 2-pyridyl stannane intermediates <strong>2 </strong>and <strong>7, </strong>which revealed optimized structure geometry and electronic energies. From the three methods that were used, M05-2X-GD3 showed the lowest mean sum of squared distances (MSSD) value and the lowest electronic energies of the hypercoordinate structures. Polymerization of the corresponding dihydrides in the presence of both early and late transition metal catalysts produced moderate molecular weight polymers <strong>10a </strong>and <strong>11a</strong>. Compound <strong>10a </strong>was cast onto a transparent film for the first time and was additionally coated on a PET film. While the cast film on PET showed good flexibility, an initial evaluation of its electronic properties using a 4-probe conductivity device revealed no intrinsic semi-conductivity. Optimization of the polymerization of <strong>10a </strong>involved a catalyst screening, using alternative dehydrocoupling catalysts. A new ethyl 2- pyridyl containing polystannane <strong>11a </strong>was synthesized with a Mw of 11,200 Da using RhCl(PPh<sub>3</sub>)<sub>3</sub>, and <sup>119</sup>Sn NMR revealed the presence of both 4- and 5-coordinate Sn centers randomly distributed along the backbone. </p>
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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 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.001 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.000 | 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 it