Synthesis, characterization, and molecular structures of nitrosyl nitrito complexes of osmium porphyrins: Disproportionation of nitric oxide in its reaction with Os(P)(CO) (P = porphyrinato dianion)
Bibliographic record
Abstract
The Os(P)(NO)(ONO) compounds (P = TTP, TMP, OEP, TmTP; TTP = 5,10,15,20-tetra-p-tolylporphyrinato dianion, TMP = 5,10,15,20-tetramesitylporphyrinato dianion, OEP = octaethylporphyrinato dianion, TmTP = tetra(m-tolyl)porphyrinato dianion) have been prepared from the reaction of the precursor carbonyl complexes Os(P)(CO) with excess nitric oxide. Nitrous oxide was detected as a by-product of the reaction. The IR spectra of the Os(P)(NO)(ONO) compounds (as KBr pellets) reveal bands in the 17901804 cm1 range that are assigned to υNO. The IR spectra also reveal two new bands for each complex in the 14951531 and 913962 cm1 ranges indicative of O-bound nitrito ligands. The linearity of the bound NO groups and the O-binding of the trans nitrito ligands in the Os(P)(NO)(ONO) complexes are evident in the single-crystal X-ray crystal structures of the TTP and TMP derivatives. The kinetics of the reaction were studied by stopped-flow mixing techniques. Spectroscopic analysis of rapidly mixed solutions of Os(P)CO and NO in toluene showed a biphasic approach to the Os(P)(NO)(ONO) and N2O products, owing to the starting material Os(P)CO scavenging CO formed during the reaction to give Os(P)(CO)2 (KCO = 106 M1). The dicarbonyl was the only transient species observed. It is proposed that the rate-determining step of the reaction leading to Os(P)(NO)(ONO) is NO displacement of CO from Os(P)(CO) via initial formation of an unstable 19 electron Os(P)(NO)(CO) intermediate.Key words: osmium, nitric oxide, X-ray, nitrosyl, porphyrin, kinetics.
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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".