Rhodium Disulfur and Dioxygen Complexes: Examination of Boron Secondary Coordination Sphere Effects
Bibliographic record
Abstract
A series of diphosphine-ligated rhodium(III) h2-peroxo and -persulfido compounds are targeted with one subset containing a boron-rich secondary coordination sphere (SCS). A systematic investigation using both experimental and theoretical methods has been performed to assess whether peripheral boranes can be used to engage with rhodium(III)-bound chalcogenides. For the model compound, [RhI(dnppe)2]BPh4 (dnppe = 1,2-bis(di-n-propylphosphino)ethane), adducts of the form [RhI(dnppe)2(h2-Ch2)]BPh4 (Ch = O or S) were characterized. For the octaboranyl compound, [RhI(P2BCy4)2]BPh4 (P2BCy4 = 1,2-bis(di(3-dicyclohexylboranyl)propylphosphino)ethane), however, treatment with O2 resulted in SCS decomposition via B—O bond formation, while reaction with 0.25 equivs. S8 provided [RhI(P2BCy4)2(2-S2)]BPh4, which based on variable-temperature 31P NMR spectroscopic measurements, does not exhibit a B—S interaction. Using a compound with a single pendant borane as a model, potential energy surface (PES) scans were found to suggest kinetic and thermodynamic feasibility of a B—O interaction with DG(B—O) = —2.5 kcal mol-1; a stationary point for the related B—S system was not located.
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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) | 0.002 | 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".