Versatile redox reactivity of triaryl-meso-substituted Ni(<scp>ii</scp>) porphyrin
Bibliographic record
Abstract
The electrochemical oxidation of nickel(ii) 5,15-p-ditolyl-10-phenylporphyrin () leads to the formation of different coupling products, with the distribution depending on the nature of the solvent (CH2Cl2-CH3CN, CH2Cl2, DMF), the cell configuration (2 or 3 compartments) and the number of electrons abstracted. In a two compartment configuration (anode and cathode in the same compartment) in a CH2Cl2-CH3CN mixture, nickel(ii) 5-chloro-10,20-p-ditolyl-15-phenylporphyrin () was isolated in good yield and its mechanism of formation is proposed. Switching to the three compartment configuration, the meso-β/meso-β doubly fused dimer () is detected as the major product whereas in pure CH2Cl2, the singly bonded meso-β dimer () is the major product; in both cases a significant amount of is also produced. These results are in accordance with the cyclic voltammetry analysis of measured in CH2Cl2-CH3CN and CH2Cl2 from which the voltammetric trace of is, respectively, appearing or not. In DMF the hydroxyporphyrin was detected as the major product. Furthermore, meso-functionalization of was performed by controlled potential electrolysis with triphenylphosphine as the nucleophile leading to the phosphonium substituted derivative () in good yield. Finally, unprecedented X-ray crystallographic structures of , , and are presented and their respective structural parameters compared.
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 | 0.000 |
| 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 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".