Binuclear Fluorovinyl Complexes of Iridium: Transformation of an Iridium-Bound Trifluorovinyl Group into a <i>trans</i>-[Ir−C(F)C(F)CH<sub>3</sub>] Moiety
Bibliographic record
Abstract
The fluorovinyl complexes [Ir 2 (CF CF 2 )(CH 3 )(CO) 2 (μ-Cl)(dppm) 2 ][CF 3 SO 3 ] ( 2 ) and [Ir 2 (C(H) CF 2 )(CH 3 )(CO) 2 (μ-Br)(dppm) 2 ][CF 3 SO 3 ] ( 3 ) are prepared by the oxidative addition of ClFC CF 2 and BrHC CF 2, respectively, to [Ir 2 (CH 3 )(CO) 2 (dppm) 2 ][CF 3 SO 3 ] ( 1 ). Both compounds have the methyl and fluorovinyl groups on different metals essentially opposite the metal−metal bond. Protonation of 2 occurs at the Ir−Ir bond to give [Ir 2 (CF CF 2 )(CH 3 )(CO) 2 (μ-Cl)(μ-H)(dppm) 2 ][CF 3 SO 3 ] 2 ( 4 ). Attempts to remove the chloride ligand from 2 or to replace it with hydride or methyl groups failed. Instead, the reaction of 2 with methyllithium resulted in replacement of one fluoride substituent on the trifluorovinyl group by a methyl group to give [Ir 2 (CF CFCH 3 )(CH 3 )(CO) 2 (μ-Cl)(dppm) 2 ][CF 3 SO 3 ] ( 5 ). The X-ray structural determination of 5 indicates that replacement of a fluoride trans to the Ir−C 2 F 3 bond has occurred and that migration of the resulting methyldifluorovinyl group to the metal bearing the methyl ligand has occurred. A proposal is put forth to rationalize these observations.
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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 | 0.000 |
| 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 | 0.001 | 0.000 |
| Research integrity | 0.001 | 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 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".