Kinetics and Thermodynamics of the Monomer−Dimer Equilibria of Dialkoxydibutylstannanes
Bibliographic record
Abstract
Enthalpies and entropies of dimerization have been determined as functions of concentration for dibutyltin dipropoxide, dibutyltin dibutoxide, and dibutyltin diisopropoxide in toluene- d 8 and cyclohexane- d 12 solutions from the variation in 119 Sn NMR chemical shifts with temperature. The values of Δ H and Δ S obtained in toluene- d 8 for dibutyltin dibutoxide were −69.5 ± 3.0 kJ mol −1 and −197 ± 10 J mol −1 K −1, respectively, and for dibutyltin diisopropoxide −67.1 ± 1.4 kJ mol −1 and −244 ± 9 J mol −1 K −1, respectively. Enthalpies and entropies of activation for this process for dibutyltin diisopropoxide have been derived by simulation of the temperature-dependent broadening of the 119 Sn NMR spectra. The free energy of activation for dimerization was 33 kJ mol −1 . The same thermodynamic parameters for a greater range of dibutyltin dialkoxides were derived theoretically by using MP2 single-point calculations on B3LYP-optimized geometries using the LANL2DZdp basis set with diffuse and polarization functions and its effective core potential for tin and 6-311G(2d,p)//6-31G(d,p) for other atoms. Quite good agreement with the experimental results was achieved with this level of theory. The present study confirms that steric effects dictate the degree of dimerization for dibutyltin dialkoxides, with monomers becoming favored at room temperature when the alkoxide groups are changed from primary to secondary.
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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 | 0.001 |
| 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 | 0.001 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| 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".