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 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) | 0.002 | 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 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".