Stoichiometric Reduction of CO<sub>2</sub> to CO by Phosphine/AlX<sub>3</sub>-Based Frustrated Lewis Pairs
Bibliographic record
Abstract
The reactions of the bulky phosphines Mes 3 P or ( o tol) 3 P with AlX 3 (X = I, Br, Cl) and CO 2 are probed and shown to give complexes of the form Mes 3 PC(OAlX 3 ) 2 (X = I ( 3 ), Br ( 4 ), Cl ( 5 )) and ( o tol) 3 PC(OAlI 3 ) 2 ( 6 ). The former compounds under CO 2 are further transformed to Mes 3 PC(OAlX 2 ) 2 OAlX 3 (X = I ( 8 ), Br ( 10 )) and [Mes 3 PX][AlX 4 ] (X = I ( 9 ), Br ( 11 )). These latter reactions are thought to proceed via dissociation of alane, as evidenced by the generation of ( o tol) 3 PC(OAl(C 6 F 5 ) 3 ) from ( o tol) 3 PC(OAl(C 6 F 5 ) 3 ) 2 ( 7 ) and the isolation of ( o tol) 3 PC(O)OAl(OC(CF 3 ) 3 ) 3 ( 15 ). Subsequent insertion of CO 2 into the Al–X bond is evidenced by the characterization of [(C 6 F 5 )C(O)OAl(C 6 F 5 ) 2 ] 2 ( 14 ) from the reaction of Al(C 6 F 5 ) 3 and CO 2 . The isolation of Al(C 6 F 5 ) 3 ·2(C 6 H 5 Br) ( 16 ) also suggests dissociation of Al(C 6 F 5 ) 3 from 7 may be facilitated by interactions with solvent. Kinetics of the formation of 8/9 from 3 show the reaction is first order in 3 and CO 2 and the rate-determining step involves an associative process. A mechanism involving dissociation of alane and subsequent insertion of CO 2 into the Al–X bond is proposed.
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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) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.001 | 0.003 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.006 | 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; both teacher heads agree on what is shown here.
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".