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
Bibliographic record
Abstract
ABSTRACT Density functional theory (DFT) calculations for the six‐membered ring 1,4‐(CH2)2(PtBu)4 (1), the dimer (PtBu2)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 12+, 3a2+, and 3b2+ 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(ORF)4]− (RF = C(CF3)3) in CH2Cl2 led to a complex mixture; the protonated cation H1+ (1,4‐(CH2)2(PtBu)3(HPtBu)+) was identified as one of the major products on the basis of multinuclear NMR spectra.
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.
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) | 0.005 | 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".