Probing the Effect of Organic and Organometallic Functionalization on [1,5]-Silicon Shifts in Indenylsilanes
Bibliographic record
Abstract
Indenylsilanes bearing organic and organometallic substituents have been prepared in order to probe the effect of substitution on the rate of [1,5]-silicon shifts in this class of compounds. In an attempt to prepare 1,1,3-tris(trimethylsilyl)indene ( 7 ), the hitherto unknown silicon-functionalized bis(trimethylsilyl)dibenzo[ a, d ]fulvalene ( 9 ) was unexpectedly generated; this species was characterized by use of both NMR spectroscopy and X-ray crystallography and was rationally prepared in 68% yield from 3,3‘-bis(1-(trimethylsilyl))indene ( 16 ). The molecular dynamics of 1,3-dimethyl-1-(trimethylsilyl)indene ( 18 ) and the crystallographically characterized chromium complex (η 6 -1,3-dimethyl-1- exo -(trimethylsilyl)indene)tricarbonylchromium ( 22 ) were examined by use of 1D-selective inversion and 2D-EXSY NMR techniques; surprisingly, the presence of chromium and methyl substituents has a negligible effect on the rate of [1,5]-silicon shifts ( Δ G ⧧ = 23−24 kcal mol - 1 ) versus the parent compound 1-(trimethylsilyl)indene ( 3 ) ( Δ G ⧧ ≈ 24 kcal mol - 1 ). In the case of 18, the intermediate isoindene 18- iso was intercepted with tetracyanoethylene as the crystallographically characterized [4 + 2] cycloadduct 5,6-benzo-2,2,3,3-tetracyano-1,4-dimethyl-7-(trimethylsilyl)bicyclo(2.2.1)hept-5-ene ( 19 ).
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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) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 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) | 0.008 | 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".