Fluorous biphasic catalysis. 2. Synthesis of fluoroponytailed amine ligands along with fluoroponytailed carboxylate synthons, [M(C<sub>8</sub>F<sub>17</sub>(CH<sub>2</sub>)<sub>2</sub>CO<sub>2</sub>)<sub>2</sub>] (M = Mn<sup>2+</sup> or Co<sup>2+</sup>): Demonstration of a perfluoroheptane soluble precatalyst for alkane and alkene functionalization in the presence of <i>tert</i>-butyl hydroperoxide and oxygen gas
Bibliographic record
Abstract
Fluorous biphasic catalysis (FBC) is a relatively new concept for homogeneous catalysis where the fluorocarbon soluble catalyst resides in a separate phase from the substrate and products. Therefore, separation of the catalyst and the products occurs by a facile decantation process. In this contribution, we present the synthesis of new R f -fluoroponytailed synthons, 2-iodo-1-perfluorooctyl-3-propanol (1), 3-perfluorooctyl-1-propanol (2), and 3-perfluorooctyl-1-iodopropane (3), a variety of new R f -fluoroponytailed ligands (48), with starting amines, 1,4,7-triazacyclononane, bis-picolylamine, and bis-picolylaminoethylenediamine, as well as new R f Mn 2+ and R f Co 2+ fluoroponytailed carboxylate synthons, [Mn(O 2 C(CH 2 ) 2 C 8 F 17 ) 2 ] (9), and [Co(O 2 C(CH 2 ) 2 C 8 F 17 ) 2 ] (10), where R f is C 8 F 17 . The only totally perfluoralkane soluble ligand we found was 1,4,7-tris-N-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoroundecyl)-1,4,7-triazacyclononane (R f TACN, 4), and it was utilized, along with synthons 9 and 10, to generate in situ R f Mn 2+ R f TACN and R f Co 2+ R f TACN complexes as precatalysts for functionalization of alkanes and alkenes. We will demonstrate that indeed this novel FBC approach for the separation of the precatalyst from the substrates and (or) products is viable for oxidation of alkanes and alkenes in the presence of the necessary oxidants, tert-butyl hydroperoxide (TBHP), and O 2 gas. We will also show that these oxidation reactions occur via an autoxidation mechanism under our FBC conditions, while using electron spin resonance (ESR) techniques to ascertain the redox chemistry occurring with the starting mononuclear R f Mn 2+ R f TACN complex.Key words: fluorous solvents, biphasic catalysis, alkane/alkene oxidation.
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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 | 0.004 | 0.002 |
| Meta-epidemiology (narrow) | 0.002 | 0.002 |
| Meta-epidemiology (broad) | 0.003 | 0.001 |
| Bibliometrics | 0.001 | 0.002 |
| Science and technology studies | 0.001 | 0.002 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.002 | 0.000 |
| Research integrity | 0.002 | 0.003 |
| Insufficient payload (model declined to judge) | 0.000 | 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; 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".