Fast Kinetic Studies of the Reactivities of Transient Germylenes in Methanol and Tetrahydrofuran Solution
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Bibliographic record
Abstract
Laser flash photolysis techniques have been employed to study the reactivities of dimethylgermylene (GeMe 2 ), diphenylgermylene (GePh 2 ), and a series of ring-substituted diarylgermylenes (GeAr 2 ) in methanol (MeOH) and tetrahydrofuran (THF) solution, where the germylenes exist as the corresponding Lewis acid−base complexes with the O-donor solvents. Dimerization to the corresponding digermene is a significant mode of decay in THF solution, particularly for the GeMe 2 −THF complex, though for the diaryl systems it is slowed dramatically compared to the situation in hexane solution. On the other hand, dimerization is undetectable in MeOH, where the GeAr 2 −MeOH complexes decay with pseudo-first-order kinetics at low laser intensities and lifetimes in the 20−50 μs range; the GeMe 2 −MeOH complex exhibits a lifetime of ca. 4 μs under similar conditions. Solvent kinetic isotope effects are consistent with solvent-catalyzed proton transfer to yield the corresponding alkoxyhydridogermane as the process responsible for the decay of the germylene−MeOH complexes. Their decay is accelerated by strong acids and bases such as methanesulfonic acid and sodium methoxide, respectively, which quench the GePh 2 −MeOH complex with rate constants of ca. 3 × 10 9 M −1 s −1 in each case. Kinetic isotope and substituent effects are consistent with rate-determining protonation at germanium in the reactions with acid, while the results for methoxide quenching are consistent with the formation of the corresponding Ar 2 (MeO)Ge − anion as a discrete intermediate, which has been detected in MeOH solution in one instance. Reaction of sodium methoxide with the germylene−THF complexes also proceeds rapidly and allows the detection of the corresponding Ar 2 (MeO)Ge − anions and determination of rate coefficients for their protonation by MeOH, for all four of the diaryl systems that were studied. The reactivity of the GeMe 2 −THF complex toward sodium methoxide, methanesulfonic and acetic acid, CCl 4, oxygen, isoprene, and 4,4-dimethyl-1-pentene has also been examined.
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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) | 0.000 | 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) | 0.000 | 0.000 |
Machine scores (provisional)
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Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
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