Formation and X-ray structure of the hostguest adduct [Pd<sub>3</sub>(dppm)<sub>3</sub>(CO)(NO<sub>3</sub>)]<sup>+</sup> and the mechanism of its electrochemical reduction
Bibliographic record
Abstract
[Pd3(dppm)3(CO)]2+, [Pd3]2+, reacts with NO3 to form the hostguest adduct [Pd3(dppm)3(CO)(NO3)]+, [Pd3(NO3)]+. The presence of NO3 inside the cavity is confirmed by X-ray crystallography. Using a qualitative relationship between λmax (UVvis) and the association constant of various adducts, the relative binding between NO3 and [Pd3]2+ is in the same order of magnitude of that between CF3CO2 and [Pd3]2+. Based on Pd···O distances, the NO3 ion is relativity more weakly associated to [Pd3]2+ in comparison with the known [Pd3(CF3CO2)]+. Using variation of [NO3] in the presence of [Pd3](PF6)2 and variation of scan rates, the resulting cyclic voltammogramms (CV) were simulated to extract both kinetic and thermodynamic constants associated to a square scheme. Both the anodic and cathodic scans of the title cluster exhibits ECE mechanisms (E = electrochemical process; C = chemical process). For the anodic scan, the EEC event is not ruled out, at least as a minor process.Key words: nitrate, palladium cluster, adduct, electrochemistry, X-ray structure, rate constant, equilibrium constant.
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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 | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.001 | 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".