Synthesis, characterization, and protonation of octaethylporphyrin osmium nitrosyl complexes containing axial thiolate ligands - X-ray structures of an alkyl thionitrite (RSNO) and its (OEP)Os(NO)(SR) addition product
Bibliographic record
Abstract
The (OEP)Os(NO)(SR) compounds (R = Me, Et, i-Pr, t-Bu) have been prepared in 33-48% isolated yields by the formal trans-addition of the precursor alkyl thionitrites (RSNO) across the metal center in (OEP)Os(CO). The nitrosyl thiolate compounds have been characterized by IR, 1H NMR, and UV-vis spectroscopy, and by FAB mass spectrometry. Their IR spectra display bands in the 1751-1755 cm-1 (KBr) range, which is indicative of terminal N-bound NO ligands in this class of compounds. The thiolate-thiol (OEP)Os(NO)(SCH2CH2SH) complex has been prepared in 70% isolated yield from the reaction of (OEP)Os(NO)(O-i-C5H11) with ethane-1,2-dithiol. Nitrosation of the free -SH group in (OEP)Os(NO)(SCH2CH2SH) with t-BuONO, followed by reaction with (TTP)Ru(CO) gave [(OEP)Os(NO)](µ-SCH2CH2S-S,S')[Ru(NO)(TTP)] in 70% yield by 1H NMR spectroscopy. The (OEP)Os(NO)(SCR'2CH2NHC(O)Me) compounds have also been prepared either by an alkoxide-thiolate exchange reaction (for R' = H) or by RSNO addition to (OEP)Os(CO) (for R' = Me). The solid-state molecular structures of the precursor RSNO thionitrite (for R' = Me) and the metalloderivative have been determined by single-crystal X-ray crystallography. Protonation of these (OEP)Os(NO)(SCR'2CH2NHC(O)Me) complexes gave the amide-bound [(OEP)Os(NO)(O=C(Me)NHCH2CR'2SH)]BF4 derivatives. The latter cationic compounds were also obtained by the sequential reaction of (OEP)Os(CO) with nitrosonium tetrafluoroborate, followed by addition of the amide-thiol reagent. Key words: thionitrite, nitrosothiol, porphyrin, X-ray structure, nitric oxide, osmium.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| 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 itClassification
machine, unvalidatedMachine predicted; a candidate call from one source (direct Gemma or distilled Codex), 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".