Photochemistry of Group 14 1,1,1-Trimethyl-2,2,2-triphenyldimetallanes (Ph<sub>3</sub>MM‘Me<sub>3</sub>; M, M‘ = Si, Ge). Direct Detection and Characterization of Silene and Germene Reactive Intermediates
Bibliographic record
Abstract
The photochemistry of trimethylsilyltriphenylgermane (Ph 3 GeSiMe 3 ), triphenylsilyltrimethylgermane (Ph 3 SiGeMe 3 ), and 1,1,1-trimethyl-2,2,2-triphenyldigermane (Ph 3 GeGeMe 3 ) has been studied in hydrocarbon solution by steady state and laser flash photolysis methods and is compared to previously reported data for the homologous disilane Ph 3 SiSiMe 3 . A variety of products are formed upon photolysis of the three compounds in the presence of 2,3-dimethyl-1,3-butadiene or chloroform, but in each case the major ones are derived from M−M‘ bond homolysis and dimethyl- or diphenylgermylene extrusion. The trapping products of the 1,3,5-(1-metalla)hexatriene derivatives formed by [1,3]-MMe 3 migration into the ortho-position of one of the phenyl rings are formed as well, in yields of 9−30%. While these experiments indicate that germylenes are formed in at least twice the yield of the 1,3,5-(1-metalla)hexatrienes, only the latter and triphenylsilyl or triphenylgermyl radicals can be detected by laser flash photolysis techniques. The metallaenes have been identified on the basis of their time-resolved UV absorption spectra and absolute rate constants for reaction with 2,3-dimethylbutadiene, methanol, acetone, acetic acid, oxygen, and carbon tetrachloride and can be distinguished from germylenes by their lack of reactivity toward triethylsilane and chloroform. Radical formation is shown to result from reaction of the triplet states of these compounds, and a triplet lifetime is estimated for Ph 3 GeSiMe 3 and compared to that of the disilane homologue. The results of time-resolved experiments on other, related compounds are discussed in light of these results.
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How this classification was reachedexpand
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) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| 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) | 0.001 | 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 teacher head, 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".