Rhodium(III) Peroxo Complexes Containing Carbene and Phosphine Ligands
Bibliographic record
Abstract
The Rh(I) carbene precursors [RhCl(COE)(NHC)] 2, where the N-heterocyclic carbene is 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) or 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes), were used to synthesize the RhCl(NHC)(P-N) complexes 4 (NHC = IPr) and 5 (NHC = IMes), where P-N is P,N-chelated o -(diphenylphosphino)- N, N -dimethylaniline, and the corresponding cis -RhCl(NHC)(PPh 3 ) 2 complexes 6 and 7 . The synthesis of 4 surprisingly requires the reaction to be carried out under a hydrogen atmosphere and occurs via the intermediate dihydride RhCl(H) 2 (IPr)(P-N) ( 3 ). Complexes 4 − 7 in benzene readily undergo irreversible oxidative addition of O 2 to form the corresponding Rh(III) peroxide complexes 9 − 12 . For comparative purposes, RhCl(PPh 3 )(P-N) ( 8 ) was synthesized from RhCl(PPh 3 ) 3, and this also added O 2 to form a peroxo complex ( 13 ). All of the complexes were generally characterized by elemental analysis and 1 H, 31 P{ 1 H}, and 13 C{ 1 H} NMR and IR spectroscopies and, in the cases of 9, 10, and 13, by X-ray crystallography.
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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 | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| 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".