Hydroperoxide-Initiated Intramolecular Insertions of NO into Metal−Carbon Bonds
Bibliographic record
Abstract
The chemical transformations of metal-bound NO groups (i.e., nitrosyl ligands) have attracted considerable attention because of both their fundamental significance and their possible biological and environmental relevance. We now report our novel discovery that an oxygen-atom transfer reagent can initiate the subsequent intramolecular insertion of bound NO into an adjacent metal−ligand bond. Specifically, we have demonstrated that treatment of the dialkyl compounds Cp*Mo(NO)(CH 2 CMe 3 ) 2 ( 1 ) and Cp*W(NO)(CH 2 SiMe 3 ) 2 ( 3 ) (Cp* = η 5 -C 5 Me 5 ) with cumene hydroperoxide induces the insertion of NO into one of their metal−carbon bonds and results in the clean formation of the η 2 -nitrosoalkane oxo complexes Cp*Mo(O)(η 2 -ONCH 2 CMe 3 )(CH 2 CMe 3 ) ( 2 ) and Cp*W(O)(η 2 -ONCH 2 SiMe 3 )(CH 2 SiMe 3 ) ( 4 ). Further treatment of complexes 2 and 4 with excess O 2 results in liberation of the nitroalkanes O 2 NCH 2 EMe 3 (E = C, Si) from the metals’ coordination spheres and formation of the dioxo alkyl complexes Cp*Mo(O) 2 (CH 2 CMe 3 ) ( 5 ) and Cp*W(O) 2 (CH 2 SiMe 3 ) ( 6 ).
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) | 0.005 | 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".