Investigations into the Reactivity and Structure of Phosphinophosphonium Cations and Related Species
Bibliographic record
Abstract
Carbon and phosphorus have often been compared owing to their diagonal relationship on the periodic table. However, relative to carbon, there remains an enormous breadth of polyphosphorus chemistry that is unexplored, particularly in the area of cationic phosphorus. A key step in the systematic and rational development of larger catenated organo-polyphosphorus cations is a fundamental understanding of the reactivity of small cationic building blocks. The smallest catenated framework in this context is the phosphinophosphonium monocation [R3P-PR2]+ (or phosphine-stabilized phosphenium cation), which can be prepared with a variety of functional groups at either phosphorus centre. This dissertation explores the diverse reactivity of chloro-substituted phosphinophosphonium cations, with a particular focus on reductive coupling as a synthetic route to novel catena-phosphorus systems. The resulting cationic frameworks are comprehensively described in terms of their diasteroisomerism, solution dynamics, and solid-state structural features. Additionally, fundamental electrochemical investigations of these diphosphorus cations are outlined as a tool for understanding and quantifying the reactivity of phosphenium cations. Finally, extension of reductive coupling methodology to the first chlorostibinophosphonium cations presents a promising outlook towards the catenation of the heavier pnictogen cations.
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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) | 0.001 | 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".