Tandem C–F and\nC–H Bond Activation in\nFluoroolefins Promoted by a Bis(diethylphosphino)methane-Bridged Diiridium\nComplex: Role of Water in the Activation Processes
Bibliographic record
Abstract
The diiridium complex [Ir<sub>2</sub>(CO)<sub>3</sub>(μ-H)(depm)<sub>2</sub>]<sup>+</sup> (<b>1</b>) reacts\nwith vinyl fluoride,\n1,1-difluoroethylene, trifluoroethylene, and tetrafluoroethylene,\nundergoing C–F bond activation in all cases, in addition to\nC–H activation in the incompletely substituted fluoroolefins.\nReaction of <b>1</b> with vinyl fluoride readily undergoes geminal\nC–F/C–H activation, resulting in the bridging vinylidene\nproduct, [Ir<sub>2</sub>(H)(CO)<sub>3</sub>(μ-CCH<sub>2</sub>)(depm)<sub>2</sub>]<sup>+</sup> (<b>2</b>). Compound <b>1</b> reacts with 1,1-difluoroethylene at subambient temperature\nto give minor amounts of [Ir<sub>2</sub>(CO)<sub>3</sub>(κ<sup>1</sup>:η<sup>2</sup>-CCH)(depm)<sub>2</sub>]<sup>+</sup> (<b>4</b>), resulting from the loss of 2 equiv of HF from\nthe fluoroolefin complex, along with a mixture of two isomers of [Ir<sub>2</sub>(C(F)CH<sub>2</sub>)(CO)<sub>3</sub>(μ-CF<sub>2</sub>CH<sub>2</sub>)(depm)<sub>2</sub>]<sup>+</sup> (<b>5a</b>/<b>5b</b>), in which 2 equiv of the olefin has been incorporated.\nCompound <b>1</b> also reacts with trifluoroethylene at −30\n°C, giving a 1:1 mix of isomers of the trifluoroethylene-bridged\nspecies [Ir<sub>2</sub>(H)(CO)<sub>3</sub>(μ-CFHCF<sub>2</sub>)(depm)<sub>2</sub>]<sup>+</sup> (<b>7a</b>/<b>7b</b>), and warming this mixture above −15 °C converts both\nisomers to two products, [Ir<sub>2</sub>(H)(CO)<sub>3</sub>(μ-CCF<sub>2</sub>)(depm)<sub>2</sub>]<sup>+</sup> (<b>8</b>), in which\nthe geminal C–F and C–H bonds in the fluoroolefin have\nbeen activated, and [Ir<sub>2</sub>(H)(CO)<sub>3</sub>(μ-CHCF<sub>3</sub>)(depm)<sub>2</sub>]<sup>+</sup> (<b>9</b>), the result\nof a [1,2]-fluoride shift to give the bridging 2,2,2-trifluoroethylidene\nmoiety. Compound <b>9</b> reacts further with a second equivalent\nof trifluoroethylene over 12 h to produce the 2,2,2-trifluoroethylidene/<i>cis</i>-difluorovinyl complex, [Ir<sub>2</sub>(C(F)CFH)(CO)<sub>3</sub>(μ-CHCF<sub>3</sub>)(depm)<sub>2</sub>]<sup>+</sup> (<b>10</b>). Finally, tetrafluoroethylene reacts with <b>1</b> to produce the bridged adduct, [Ir<sub>2</sub>(H)(CO)<sub>3</sub>(μ-CF<sub>2</sub>CF<sub>2</sub>)(depm)<sub>2</sub>]<sup>+</sup> (<b>11</b>), followed by a single C–F activation to\ngive [Ir<sub>2</sub>(C(F)CF<sub>2</sub>)(CO)<sub>3</sub>(depm)<sub>2</sub>]<sup>+</sup> (<b>12</b>). The roles of the hydride\nligand and exogenous water in the C–F activation processes\nare discussed.
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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 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.002 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.013 | 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".