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
[Pd 3 (dppm) 3 (CO)] 2+ , [Pd 3 ] 2+ , reacts with NO 3 to form the hostguest adduct [Pd 3 (dppm) 3 (CO)(NO 3 )] + , [Pd 3 (NO 3 )] + . The presence of NO 3 inside the cavity is confirmed by X-ray crystallography. Using a qualitative relationship between λ max (UVvis) and the association constant of various adducts, the relative binding between NO 3 and [Pd 3 ] 2+ is in the same order of magnitude of that between CF 3 CO 2 and [Pd 3 ] 2+ . Based on Pd···O distances, the NO 3 ion is relativity more weakly associated to [Pd 3 ] 2+ in comparison with the known [Pd 3 (CF 3 CO 2 )] + . Using variation of [NO 3 ] in the presence of [Pd 3 ](PF 6 ) 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 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 | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 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 | 0.000 | 0.001 |
| 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 itClassification
machine, unvalidatedMachine predicted; a candidate call from one teacher head, 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".