Facile Carbon–Carbon Bond Formation and Multiple Carbon–Hydrogen Bond Activations Promoted by Methylene-Bridged Iridium/Ruthenium Complexes
Bibliographic record
Abstract
The methylene-bridged complex [IrRu(CO) 4 (μ-CH 2 )(dppm) 2 ][BF 4 ] ( 1; dppm = μ-Ph 2 PCH 2 PPh 2 ) reacts with 1,1-dimethylallene and 1,2-butadiene, resulting in coupling of the cumulene and the bridging methylene group, yielding the complexes [IrRu(CO) 4 (κ 1:κ 1 -Me 2 C═ C CH 2 C H 2 )(dppm) 2 ][BF 4 ] ( 2 ) and [IrRu(CO) 4 (κ 1:κ 1 -MeCH═ C CH 2 C H 2 )(dppm) 2 ][BF 4 ] ( 3 ), respectively, in which the resulting hydrocarbyl fragment is chelating on iridium. Reaction of 1 with 1,1-difluoroallene initially yields the analogous insertion product [IrRu(CO) 4 (κ 1:κ 1 -F 2 C═ C CH 2 C H 2 )(dppm) 2 ][BF 4 ] ( 6 ), which slowly converts to [IrRu(CO) 3 (κ 1:κ 1 -F 2 C═ C CH 2 CH 2 C O)(dppm) 2 ][BF 4 ] ( 7 ) by carbonyl migratory insertion. Reaction of 1 with propadiene leads to the elimination of 1,3-butadiene and the formation of [IrRu(CO) 4 (dppm) 2 ][BF 4 ]. In the presence of excess 1,1-dimethylallene, compound 2 reacts further via multiple C–H bond activations to yield [IrRu(CO) 3 (κ 1 -C(CH 2 CH 3 )═C(CH 3 ) 2 )(μ-κ 1:η 2 -C≡CC(CH 3 )═CH 2 )(dppm) 2 ][BF 4 ] ( 8 ) with the elimination of H 2, together with [IrRu(CO) 3 (κ 1 -C(CH 2 CH 3 )═C(CH 3 ) 2 )(μ-κ 1:η 2 -C≡CCH(CH 3 ) 2 )(dppm) 2 ][BF 4 ] ( 9 ). Complex 2 also reacts with propadiene to generate [IrRu(CO) 3 (κ 1 -C(CH 2 CH 3 )═C(CH 3 ) 2 )(μ-κ 1:η 2 -C≡CCH 3 )(dppm) 2 ][BF 4 ] ( 10 ) and with 1,2-butadiene to yield [IrRu(CO) 3 (κ 1 -C(CH 2 CH 3 )═C(CH 3 ) 2 )(μ-κ 1:η 2 -C≡CCH 2 CH 3 )(dppm) 2 ][BF 4 ] ( 11 ) and [IrRu(CO) 3 (κ 1 -C(CH 2 CH 3 )═C(CH 3 ) 2 )(μ-κ 1:η 2 -C≡CCH═CH 2 )(dppm) 2 ][BF 4 ] ( 12 ).
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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 | 0.001 |
| Meta-epidemiology (narrow) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| 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) | 0.001 | 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 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".