Preparation of hydrido(vinyl)iridium(III) complexes from functionalized olefins by CH activation
Bibliographic record
Abstract
The four-coordinate iridium(I) precursor trans-[IrCl(N 2 )(PPh 3 ) 2 ] (1) reacts with functionalized olefins RCH=C(R′)C(O)R′′ by displacement of the dinitrogen ligand and oxidative addition of the CH bond to the metal center to give six-coordinate hydrido(vinyl)iridium(III) complexes [IrH(Cl){κ 2 (C,O)-C(R)=C(R′)C(R′′)=O}(PPh 3 ) 2 ] (212) in good to excellent yields. The reaction of [IrH(Cl){κ 2 (C,O)-CH=CHC(Me)=O}(PPh 3 ) 2 ] (2) with AgClO 4 affords the cationic compound [IrH{κ 2 (C,O)-CH=CHC(Me)=O}(PPh 3 ) 2 ]ClO 4 (15), which in solution equilibrates with the uncharged isomers [IrH(OClO 3 ){κ 2 (C,O)-CH=CHC(Me)=O}(PPh 3 ) 2 ] (15a and 15b). In contrast, five-coordinate [IrH{κ 2 (C,O)-CH=CHC(Et)=O}(PPh 3 ) 2 ]ClO 4 (16), prepared from 3 and AgClO 4 , is stable and undergoes addition reactions with CO, PPh 3 , C 2 H 4 , CH 3 C≡CH, MeCN, and PhCN to give the six-coordinate complexes [IrH(L){κ 2 (C,O)-CH=CHC(Et)=O}(PPh 3 ) 2 ]ClO 4 (1722). The neutral hydrido(thiolato) compound [IrH(SPh){κ 2 (C,O)-CH=CHC(Et)=O}(PPh 3 ) 2 ] (23) was obtained on treatment of 21 with NaSPh. Key words: iridium, CH activation, hydrido complexes, vinyl complexes, phosphine complexes.
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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 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.007 | 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".