Photo-Redox Mechanism for the Reaction of “Cation-like” Zirconocene Silyl Complexes with Silanes
Bibliographic record
Abstract
A kinetic study of the photochemical reaction of [Cp 2 Zr(μ-SiH 2 Ph)] 2 2+ 2[BBu n (C 6 F 5 ) 4 - n ] - ( 1 ) with PhCH 2 SiH 3 to give the analogous PhCH 2 SiH 2 complex 2 was carried out using a combination of NMR and EPR spectroscopy to follow the rates of disappearance of reactants and the appearance of intermediates and products. The paramagnetic intermediate [Cp 2 Zr III ] + [BBu n (C 6 F 5 ) 4 - n ] - ( 3 ) is produced with a quantum efficiency of 0.96 ± 0.16 on irradiation of 1 with light having λ < 450 nm. The rate law and analysis of intermediates supports a Zr(IV)/Zr(III) redox mechanism in which the rate-determining step is photodecomposition of 1 to generate 3 and silyl radicals by homolytic dissociation. In the presence of excess PhCH 2 SiH 3 3 reacts rapidly to give products.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
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 | 0.000 |
| 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) | 0.002 | 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".