Iminophosphorano‐Substituted Bispyridinylidenes: Redox Potentials and Substituent Constants from Tolman Electronic Parameters
Bibliographic record
Abstract
Abstract Bispyridinylidenes (BPYs) have emerged as an important class of neutral organic electron donors, with redox potentials that vary widely with choice of substituent. Methods to predict the effect of substitution on the redox potential are therefore highly desirable. Here we show that the redox potential of BPYs featuring iminophosphorano substituents (R 3 P=N‐), which represent the most reducing class of BPYs, can be predicted based on the well‐known Tolman electronic parameter (TEP) for the respective phosphine fragment (R 3 P). Moreover, building on earlier work relating redox potentials to Hammett‐type substituent constants, it is now possible to quantitatively predict σ p + values for iminophosphorano substituents from TEP values. These results provide a path for precisely tailoring redox potentials of iminophosphorano‐substituted BPYs, but also give quantitative descriptors for how these highly versatile iminophosphorano substituents can impact the properties of any molecular scaffold.
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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 | 0.001 |
| 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 | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.003 | 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".