Kinetic and mechanistic studies of the reactions of diarylgermylenes and tetraaryldigermenes with carbon tetrachloride
Bibliographic record
Abstract
The mechanisms of the reactions of diphenylgermylene (GePh2) with CCl4 in hydrocarbon solvents and in THF solution have been studied, employing 3,4-dimethyl-1,1-diphenylgermacyclopent-3-ene (6a) and 1,1-diphenylgermacyclobutane (17) as photochemical precursors to GePh2. In hydrocarbon solvents, the reaction produces Ph2GeCl2 (10) and Ph2Ge(Cl)CCl3 (12) in a ratio of 10:12 ≈ 7, along with a variety of other radical-derived products and small amounts of Ph2GeH(D)Cl (11), which is formed partly by reaction of GePh2 with adventitious HCl. The reaction is much cleaner in THF, where 12 is formed as the major product (10:12 ≈ 0.8); a similar product distribution is obtained in hexanes containing 0.05 mol/L THF, while 12 is the exclusive product in hexanes containing 3 mmol/L NEt3. Rate constants for the reactions of CCl4 with GePh2 and five ring-substituted derivatives were determined by laser flash photolysis, as well as Arrhenius parameters for reaction of the parent (GePh2), in the two solvents. The reactions of GePh2 with CCl4 and CHCl3 have also been studied in 3-methylpentane solution at 78–90 K. Different reaction mechanisms are clearly operative in hydrocarbon and complexing solvents, but both involve modest charge donation from germanium to the substrate in the transition state for the rate-determining step. For the reaction in hydrocarbon solvents, the data are consistent with inner-sphere electron transfer following or in concert with weak Lewis acid–base complexation. A similar mechanism is proposed for the reaction in THF solution, in competition with a second involving nucleophilic attack of the germylene–THF complex at a chlorine atom of the substrate. Rate constants were also determined for reaction of CCl4 with the corresponding tetraaryldigermenes at low halocarbon concentrations in hexanes, along with Arrhenius parameters for the parent (Ge2Ph4). These reactions also proceed via initial Cl-atom abstraction, based on the identity of the products formed in the reaction of CCl4 with tetramesityldigermene.
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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 | 0.000 |
| Insufficient payload (model declined to judge) | 0.002 | 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 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".