Experimental and theoretical studies of the standard oxidation potentials of triethylamine and triethanolamine
Bibliographic record
Abstract
Tertiary aliphatic amines epitomized by triethylamine and triethanolamine (TEOA) are sacrificial donors used in photocatalytic CO 2 reductions in acetonitrile. Knowing their standard oxidation potential ( E 0 ox ) in acetonitrile helps design efficient catalytic systems. However, reported values either do not exist or do not agree with each other. We determined the values to be 1.05 and 1.21 V (vs. aqueous NHE) by the inflection-point method (Vullev et al. J. Electrochem. Soc., 2019, H3175), which agrees very well with the calculated results (1.09 and 1.20 V, respectively) using the M06SMD-s method, we presented in this work. To calculate E 0 ox values, we proposed three methods at M06-2X/6-31G * level without using thermodynamic cycles. They differ in the way of calculating free energies in solvent ( G s ). All of them are accurate; however, the M06SMD-s method is the most efficient. It obtains the related G s based on single-point calculations of the gas-phase geometries using the SMD solvent model. The calculated E 0 ox values for seven benzene derivatives and five N-containing compounds are very accurate with an average absolute error of 30 mV. In addition, our calculations reveal that TEOA molecules can associate with each other through hydrogen bonds. The standard equilibrium constant ( K 0 ) for forming the dimer reaches 1.63 × 10 6 . Furthermore, we proved that the E 0 (Fc + /Fc) (Fc = ferrocene) to be 0.629 V versus NHE, which can be obtained accurately using a wide range of conditions. The Ag + /Ag (Ag|0.010 M AgNO 3 , 0.090 M [NBu 4 ]PF 6 ) reference electrode potential was determined to be 0.544 V (NHE).
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
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) | 0.000 | 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) | 0.001 | 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 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".