Structural Changes Upon Oxidation of (P<sup>t</sup>Bu<sub>2</sub>)<sub>2</sub> and 1,4‐(CH<sub>2</sub>)<sub>2</sub>(P<sup>t</sup>Bu)<sub>4</sub>: Transannular P–P Interactions in Cations of the 1,4‐C<sub>2</sub>P<sub>4</sub> Ring
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Bibliographic record
Abstract
ABSTRACT Density functional theory (DFT) calculations for the six‐membered ring 1,4‐(CH 2 ) 2 (P t Bu) 4 ( 1 ), the dimer (P t Bu 2 ) 2 ( 2 ) and the 2,5‐chalcogenated derivatives of 1 , 3a (E = S) and 3b (E = Se), and the corresponding cation radicals and dications predict significant structural changes upon oxidation. The formation of a transannular P–P single bond (ca. 2.25 Å) in the three cyclic dications 1 2+ , 3a 2+ , and 3b 2+ is indicated by geometry and consideration of the frontier orbitals. The calculations also indicate a weak transannular interaction in the cyclic cation radicals. The nature of these transannular P–P bonding interactions is analyzed through a consideration of the molecular orbitals involved. Cyclic Voltammetry studies of 1 and 2 reveal two well‐separated oxidation processes. Both processes are irreversible for 1 at normal scan rates, whereas for 2 the first process is quasi‐reversible. The cation radical 1 +• could not be detected by in situ electron paramagnetic resonance studies of the first electrochemical oxidation, but a spectrum for the radical cation 2 +• could be observed. The difference in the redox behavior of 1 and 2 is considered with respect to the structural parameters and DFT calculations. Chemical oxidation of 1 with NO + [Al(OR F ) 4 ] − (R F = C(CF 3 ) 3 ) in CH 2 Cl 2 led to a complex mixture; the protonated cation H 1 + (1,4‐(CH 2 ) 2 (P t Bu) 3 (HP t Bu) + ) was identified as one of the major products on the basis of multinuclear NMR spectra.
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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 | 0.003 | 0.002 |
| Meta-epidemiology (narrow) | 0.005 | 0.005 |
| Meta-epidemiology (broad) | 0.006 | 0.003 |
| Bibliometrics | 0.002 | 0.004 |
| Science and technology studies | 0.002 | 0.002 |
| Scholarly communication | 0.001 | 0.003 |
| Open science | 0.004 | 0.002 |
| Research integrity | 0.003 | 0.005 |
| 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 it