Amine-tethered <i>N</i>-heterocyclic carbene complexes of rhodium(I)
Bibliographic record
Abstract
A new family of rhodium-diene based complexes has been developed that incorporates an N-heterocyclic carbene ligand with an N-donor tether. The ligand is denoted Mes[CNH] 2 (where Mes[CNH] is 2,4,6-Me3C6H2NC3H2NCH2CH2NH-2,4,6-Me3C6H2) and Mes[CN] for the amido form. The synthesis of the Mes[CNH] ligand involves reaction of N-mesitylimidazole with 2-chloroethyl-N-mesitylamine under melt conditions, followed by deprotonation with KN(SiMe3)2. The reaction of Mes[CNH] with [(diene)RhCl]2 results in the formation of the monodentate complexes, Mes[CNH]Rh(diene)Cl (where diene = 1,5-cyclooctadiene (COD): 3a; diene = 2,5-norbornadiene (NBD): 3b). Bidentate variants could be isolated as either a neutral species, Mes[CN]Rh(diene) 4a–4b, via deprotonation, or an ionic analogue such as [Mes[CNH]Rh(diene)]BF4 5a–5b by reaction with NaBF4. Compounds 4–5 are the first examples of rhodium compounds that contained a bidentate NHC ligand with a pendant amino or amido donor. Complexes 3–5 were characterized fully and the solid-state single crystal X-ray structures of 3a, 4a, and 5b are discussed. The utility of these complexes as catalyst precursors for hydrogenation reactions was examined and it was determined that these systems are not significantly more active than colloidal rhodium when parallel reactions were run. Various methods of transfer hydrogenations were also investigated with 3a, which did not yield an appreciable conversion of either benzophenone or N-benzylideneaniline as substrates.Key words: rhodium, N-heterocyclic carbene, catalysis, hydrogenation.
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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 | 0.000 |
| 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".