Ethylene Substitution in a Bis-Ethylene Complex of Rh/Os and Unusual Brønsted−Lowry Basicity of an N-Heterocyclic Carbene
Bibliographic record
Abstract
Reactions of the bis-ethylene complex [RhOs(η 2 -C 2 H 4 ) 2 (μ-CO) 2 (dppm) 2 ][CF 3 SO 3 ], with CO, MeCN, PMe 3, IMe 4, and [PPN][Cl] (IMe 4 = 1,3,4,5-tetramethylimidazol-2-ylidene; PPN + = bis(triphenylphosphine)iminium) yield the monoethylene products [RhOsL(C 2 H 4 )(μ-CO) 2 (dppm) 2 ][CF 3 SO 3 ] (L = CO ( 2 ), MeCN ( 3 ), PMe 3 ( 4 ), IMe 4 ( 5 )) and [RhOsCl(C 2 H 4 )(μ-CO) 2 (dppm) 2 ] ( 6 ), respectively, by substitution of the Rh-bound ethylene ligand. In the case of L = CO, carbon monoxide was added at −78 °C, since at higher temperatures substitution of both ethylene ligands occurred to give the known product [RhOs(CO) 4 (dppm) 2 ][CF 3 SO 3 ]. For L = IMe 4, the stoichiometry had to be carefully controlled, since in the presence of more than 1 equiv of IMe 4 deprotonation of a dppm methylene group by IMe 4 occurred to yield [RhOs(IMe 4 )(C 2 H 4 )(μ-CO) 2 (Ph 2 PCHPPh 2 )(dppm)]. The IMe 4 product ( 5 ) could also be obtained in THF solution by substitution of the acetonitrile ligand in compound 3 . However, when this reaction was carried out in acetonitrile, deprotonation of the acetonitrile ligand by IMe 4 occurred to give the acetonitrilide intermediate [RhOs(NCCH 2 )(C 2 H 4 )(μ-CO) 2 (dppm) 2 ], which rapidly coupled with another 1 equiv of 3 to yield the enamino−nitrile-bridged product [(RhOs(C 2 H 4 )(μ-CO) 2 (dppm) 2 ) 2 (μ-NHC(CH 3 )CHCN)][CF 3 SO 3 ].
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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 | 0.000 |
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".