Metallocenes as references for the determination of redox potentials by cyclic voltammetry Permethylated iron and cobalt sandwich complexes, inhibition by polyamine dendrimers, and the role of hydroxy-containing ferrocenes
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Bibliographic record
Abstract
Measurement of the redox potentials (E 1/2 ) of ferrocene (1), decamethylferrocene (2), decamethylcobaltocene (3), and [Fe I Cp*(η 6 -C 6 Me 6 )] (4) (Cp* = η 5 -C 5 Me 5 ) in DMF, CH 3 CN, THF, DME, CH 2 Cl 2 , and DMSO were recorded vs. the saturated calomel electrode (SCE), showing that the E 1/2 value of 1 was more solvent dependent than those of 24, and that the difference in E 1/2 values among 24 was solvent independent, unlike those found between 1 and 24. This shows that 24 are much more reliable internal references for determining redox potentials than 1, but using data from this article, one can convert the literature values reported vs. 1 into values vs. 2, 3, or 4. The electrochemistry of 1 and 2 is all the more inhibited by polyamine dendrimers as the dendrimer generation is higher. On the other hand, ferrocenes or other iron sandwich compounds containing hydroxy groups can reestablish reversible cyclic voltammograms. It is shown, using a tetra(ferrocenylmethylamine), that this phenomenon is due to hydrogen bonding between the amido and phenol groups rather than bonding of hydroxy groups to the electrode surface.Key words: ferrocene, reference, electrochemistry, metallocene, sandwich complex, iron, dendrimer, passivation, hydrogen bond.
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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) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| 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 it