Experimental and Theoretical Investigations of the Redox Behavior of the Heterodichalcogenido Ligands [(EP<sup>i</sup>Pr<sub>2</sub>)(TeP<sup>i</sup>Pr<sub>2</sub>)N]<sup>−</sup>(E = S, Se): Cyclic Cations and Acyclic Dichalcogenide Dimers
Bibliographic record
Abstract
The two-electron oxidation of the lithium salts of the heterodichalcogenidoimidodiphosphinate anions [(EP (i)Pr 2)(TeP (i)Pr 2)N] (-) ( 1a, E = S; 1b, E = Se) with iodine yields cyclic cations [(EP (i)Pr 2)(TeP (i)Pr 2)N] (+) as their iodide salts [(SP (i)Pr 2)(TeP (i)Pr 2)N]I ( 2a) and [(SeP (i)Pr 2)(TeP (i)Pr 2)N]I ( 2b). The five-membered rings in 2a and 2b both display an elongated E-Te bond as a consequence of an interaction between tellurium and the iodide anion. One-electron reduction of 2a and 2b with cobaltocene produces the neutral dimers (EP (i)Pr 2NP (i)Pr 2Te-) 2 ( 3a, E = S; 3b, E = Se), which are connected exclusively through a Te-Te bond. Two-electron reduction of 2a and 2b with 2 equiv of cobaltocene regenerates the corresponding dichalcogenidoimidodiphosphinate anions as ion-separated cobaltocenium salts Cp 2Co[(EP (i)Pr 2)(TeP (i)Pr 2)N] ( 4a, E = S; 4b, E = Se). The ditellurido analogue Cp 2Co[(TeP (i)Pr 2) 2N] ( 4c) has been prepared in the same manner for comparison. Density functional theory calculations reveal that the preferential interaction of the iodide anion with tellurium is determined by the polarization of the lowest unoccupied molecular orbital [sigma*(E-Te)] of the cations in 2a and 2b toward tellurium and that the formation of the dimers 3a and 3b with a central Te-Te linkage is energetically more favorable than the structural isomers with either E-Te or E-E bonds. Compounds 2a, 2b, 3a, 3b, 4a, 4b, and 4c have been characterized in solution by multinuclear NMR spectroscopy and in the solid state by X-ray crystallography.
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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 | 0.001 |
| 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 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.006 | 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".