The one-electron reduction of dithiolate and diselenolate ligands
Bibliographic record
Abstract
Herein we present an assessment to determine which of nine well-established DFT functionals best describes the reduction of C2H2Se2(-)˙. In addition, we have also studied the effects of changing the substituents bound to the alkene functional group of dithiolene and diselenolene ligands. Such ligands are important due to their unique electrochemical and physical properties when ligated to metals. The M06-L functional shows best agreement with the QCISD/cc-pVTZ value of -2.45 V for the reduction potential of the (C2H2Se2˙(-)/C2H2Se2(-2)) redox couple. At the M06-L/6-311+G(d,p) level of theory the calculated reduction potential for the (C2H2Se2˙(-)/C2H2Se2(-2)) redox couple is only 0.09 V in error. However, as a result of the nature of the oxidized species for the respective ligands the absolute reduction potential of the (C2H2Se2˙(-)/C2H2Se2(-2)) redox couple is 0.57 V more oxidizing than the (C2H2S2˙(-)/C2H2S2(-2)) redox couple. This is due to the radical electron in C2H2S2˙(-) being delocalized within the alkene backbone, whereas in C2H2Se2˙(-) the electron is largely localized on the Se atoms. The relative reducing power of the S- and Se-containing redox couples is shown to vary depending on the choice of substituents. In particular the reduction potential of the various S-containing redox couples range from being 0.34 V more reducing to 0.28 V more oxidizing than the analogous Se-containing redox couples. This difference in the relative reducing power appears to be a result of the nature of the oxidized ligand. Thus, depending on the choice of moiety very different chemistry is seen between the analogous dithiolate and diselenolate ligands.
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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 | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.002 | 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".