Generation and dissociation of oxygen‐ and chloride‐bridged iron(III) and manganese(III) tetraphenylporphyrin dimer ions in the gas phase
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Bibliographic record
Abstract
Electrospray ionization mass spectrometry (ESI/MS) has allowed the discovery of novel dimer ions emerging from solutions of metalloporphyrin salts and their investigation by collision-induced dissociation (CID) with N(2) molecules. ESI mass spectra have been recorded for the formation of the oxygen or chloride-bridged dimer ions [(FeTPP)(2)OH](+), [(MnTPP)(2)OH](+), [(FeTPP)(2)Cl](+) and [(MnTPP)(2)Cl](+) derived from various solutions of FeTPPCl and MnTPPCl salts. The CID of [(FeTPP)(2)OH](+) proceeds mainly by neutral loss of (FeTPP)OH to form [FeTPP](+) and, to a minor extent, to form the charge-reversed products. The CID of [(MnTPP)(2)OH](+) exhibits exclusively the product ion [MnTPP](+) by loss of neutral (MnTPP)OH. [(FeTPP)(2)Cl](+) and [(MnTPP)(2)Cl](+) dissociate by loss of (Fe/MnTPP)Cl to give rise to [Fe/MnTPP](+). [(FeTPP)(2)O](+) and [(FeTPP)(2)OH](+) were generated from a solution of the dimer, (FeTPP)(2)O. Dissociation of [(FeTPP)(2)O](+) yields two product ions, [FeTPP](+) and [(FeTPP)O](+), with higher onsets compared to the equivalent fragments formed from [(FeTPP)(2)OH](+).
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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 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.000 | 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