New insights into phosphorus biphilicity: Stereochemistry of monocyclic aminophosphoranes formation
Why this work is in the frame
A frame that forgets how it found something cannot be audited. These are the routes that admitted this work.
Bibliographic record
Abstract
Abstract Oxidative addition of aliphatic amine on monocyclic 2‐R‐1,3,2‐dioxaphospholane (R = methyl or phenyl) leading to phosphoranes bearing a PH axial bond was investigated using a combined theoretical and experimental approach. The reaction followed first order kinetics for both reactants. The activation parameters were consistent with a concerted mechanism exhibiting stereo, enantio, and regio specificities. Systematic density functional theory studies including reactivity descriptors, structural parameters, determination of all possible phosphorane isomers, their transition states and their formation mechanisms were carried out to delineate the reaction pathway. Depending on the nature of the atom in the final apical position (H, N of the amine, or C of the methyl), three types of phosphoranes were identified. Energy profiles, using the intrinsic reaction coordinate technique for the formation of each isomer, were established. It was shown that the phosphorus biphilicity acts in three consecutive sequences, namely nitrogen nucleophilic attack leading to a supermolecule structure, nucleophilic behavior of phosphorus in the transition state zone of influence, and electrophilic approach of the nitrogen atom to complete the reaction. Phosphorane with an equatorial PH bond was found to be a kinetic product that transforms rapidly to the thermodynamically stable isomer with axial PH via two consecutive Berry pseudo‐rotations. A new tool, referred to reactive internal reaction coordinates, was introduced to represent the reaction path more clearly.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
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) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.002 | 0.001 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.004 | 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 it