Rhodium(III) Peroxo Complexes Containing Carbene and Phosphine Ligands
Why this work is in the frame
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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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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) | 0.001 | 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 it