Octahedral perfluoroalkyl complexes of Ir(III) formed by oxidative addition of perfluoroalkyl iodides to Ir(acac)(CO)<sub>2</sub>
Bibliographic record
Abstract
Oxidative addition of primary, secondary, or benzylic perfluoroalkyl iodides (RF–I) to the phosphine free Ir(I) precursor Ir(acac)(CO)2 1 (acac = 2,4-pentanedionato) proceeds smoothly to afford octahedral Ir(III) products Ir(acac)(I)(RF)(CO)2, A combination of X-ray crystallographic studies and solution spectroscopy shows that these products are the result of overall trans-addition of the C–I bond to iridium, probably a result of thermodynamic control; evidence for a kinetic product resulting from net cis-addition is obtained in one case. Treatment of the Ir(III) compounds with AgOTf (Tf = CF3SO3) illustrates that the iodo ligand is replaced by triflate with retention of stereochemistry at Ir. The resulting triflate complexes are inert to displacement by H2O or H2. The Ir(III) products exhibit very high CO stretching frequencies in the IR, indicating that the CO ligands may be non-classical. A quantitative estimation of the degree of backbonding to the CO ligands in these compounds, and a comparison of the π-acceptor properties of CO and fluoroalkyl ligands, is made using an approach based on Density Functional Theory (DFT) and Natural Bond Orbital analyses.Key words: iridium, fluoroalkyl, oxidation, carbonyl, DFT.
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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 | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.003 | 0.001 |
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".