Reactions of Rh<sub>2</sub>(CH<sub>3</sub>COO)<sub>4</sub>with thiols and thiolates: a structural study
Bibliographic record
Abstract
The structural differences between the aerobic reaction products of Rh 2 (AcO) 4 ( 1 ; AcO − = CH 3 COO − ) with thiols and thiolates in non-aqueous media are probed by X-ray absorption spectroscopy. For this study, ethanethiol, dihydrolipoic acid (DHLA; a dithiol) and their sodium thiolate salts were used. Coordination of simple thiols to the axial positions of Rh 2 (AcO) 4 with Rh—SH bonds of 2.5–2.6 Å keeps the Rh II —Rh II bond intact (2.41 ± 0.02 Å) but leads to a colour change from emerald green to burgundy. Time-dependent density functional theory (TD-DFT) calculations were performed to explain the observed shifts in the electronic (UV–vis) absorption spectra. The corresponding sodium thiolates, however, break up the Rh 2 (AcO) 4 framework in the presence of O 2 to form an oligomeric chain of triply S-bridged Rh(III) ions, each with six Rh—S (2.36 ± 0.02 Å) bonds. The Rh III ...Rh III distance, 3.18 ± 0.02 Å, in the chain is similar to that previously found for the aerobic reaction product from aqueous solutions of Rh 2 (AcO) 4 and glutathione (H 3 A), {Na 2 [Rh 2 III (HA) 4 ]·7H 2 O} n , in which each Rh(III) ion is surrounded by about four Rh—S (2.33 ± 0.02 Å) and about two Rh—O (2.08 ± 0.02 Å). The reaction products obtained in this study can be used to predict how dirhodium(II) tetracarboxylates would react with cysteine-rich proteins and peptides, such as metallothioneins.
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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 | 0.001 | 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 | 0.000 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.000 | 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".