Activation of H2 using P/Al based frustrated Lewis pairs and reactions with olefins
Bibliographic record
Abstract
The activation of H2 using Mes3P-AlX3 (X = Cl, Br, I) FLPs was investigated. Heating a 1 : 2 mixture of Mes3P-AlI3 under H2 afforded [Mes3PH][H(AlI3)2] 1. The alane Al(p-C6F4H)32 was prepared and a 1 : 2 solution of (otol)3P and 2 under H2 generated the salt [(otol)3PH][(μ-H)(Al(p-C6F4H)3)2] which could not be isolated. However, the bulky anion salt [Li(OEt2)][FAl(C12F9)3] was readily converted to [Et4N][FAl(C12F9)3] 3 and subsequently to the hydride salt [Et4N][HAl(C12F9)3] 4. Further reaction of 4 with [CPh3][B(C6F5)4] generated the free alane, Al(C12F9)3 which in the presence of Mes3P and exposure to H2 resulted in the formation of [Mes3PH][(μ-H)(Al(C12F9)3)2] 5. Exposing a solution of 1 in C6D5Br with ethylene, propylene or cyclohexene followed by quenching with water resulted in liberation of ethane, propane, or cyclohexane, respectively. In contrast, exposure of 5 to an atmosphere of ethylene showed no evidence of reaction. In related chemistry, protonation of [Et4N][EtAl(C6F5)3] by the phosphonium salts [R3PH][Al(C6F5)4] (R = otol (6), Mes (7), tBu (8)) and [(2,6-Cl2C6H3)3PH][AlCl4] (9) was also examined. In the case of the reaction of 6 and 9 ethane was liberated whereas with 7 and 8, no reaction occurred. The implications for transition metal-free hydrogenation catalysis are considered.
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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) | 0.005 | 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".