Synthesis and Characterization of Cationic Rhodium Peroxo Complexes
Bibliographic record
Abstract
Mononuclear cationic rhodium complexes of dioxygen have been synthesized and characterized. Crystallographic, spectroscopic, and computational results support the conclusion that these complexes are best described as Rh III {O 2 2– } (rhodium(III) peroxo) complexes, in contrast to recently reported neutral analogues that are best described as Rh I { 1 O 2 } adducts. The nature of the ligand trans to the O 2 ligand is crucial in defining the electronic nature of the RhO 2 bonding. It is determined that π-donor ligands such as the halides—in conjunction with sufficient steric bulk—can stabilize the formation of Rh I { 1 O 2 } adducts, whereas stronger field ligands lead to the stabilization of asymmetric O 2 binding that ultimately favors formation of higher coordinate Rh III peroxo species. The factors that control the relative stabilization of Rh III {O 2 2– } versus Rh I { 1 O 2 } species are related to the well-established Dewar–Chatt–Duncanson model that has been successfully used to describe the bonding in isoelectronic transition-metal alkene complexes. The specific factors that control the stabilization of one electromer (resonance structure) over another are explored and discussed in detail.
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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 | 0.001 |
| 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 | 0.001 |
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".