3‐Rhoda‐1,2‐diazacyclopentanes: A Series of Novel Metallacycle Complexes Derived From CN Functionalization of Ethylene
Bibliographic record
Abstract
Rh-containing metallacycles, [(TPA)Rh(III)(κ(2)-(C,N)-CH2CH2(NR)2-]Cl; TPA = N,N,N,N-tris(2-pyridylmethyl)amine have been accessed through treatment of the Rh(I) ethylene complex, [(TPA)Rh(η(2)-CH2CH2)]Cl ([1]Cl) with substituted diazenes. We show this methodology to be tolerant of electron-deficient azo compounds including azo diesters (RCO2N=NCO2R; R = Et [3]Cl, R = iPr [4]Cl, R = tBu [5]Cl, and R = Bn [6]Cl) and a cyclic azo diamide: 4-phenyl-1,2,4-triazole-3,5-dione (PTAD), [7]Cl. The latter complex features two ortho-fused ring systems and constitutes the first 3-rhoda-1,2-diazabicyclo[3.3.0]octane. Preliminary evidence suggests that these complexes result from N-N coordination followed by insertion of ethylene into a [Rh]-N bond. In terms of reactivity, [3]Cl and [4]Cl successfully undergo ring-opening using p-toluenesulfonic acid, affording the Rh chlorides, [(TPA)Rh(III)(Cl)(κ(1)-(C)-CH2CH2(NCO2R)(NHCO2R)]OTs; [13]OTs and [14]OTs. Deprotection of [5]Cl using trifluoroacetic acid was also found to give an ethyl substituted, end-on coordinated diazene [(TPA)Rh(III)(κ(2)-(C,N)-CH2CH2(NH)2-](+) [16]Cl, a hitherto unreported motif. Treatment of [16]Cl with acetyl chloride resulted in the bisacetylated adduct [(TPA)Rh(III)(κ(2)-(C,N)-CH2CH2(NAc)2-](+), [17]Cl. Treatment of [1]Cl with AcN=NAc did not give the Rh-N insertion product, but instead the N,O-chelated complex [(TPA)Rh(I)(κ(2)-(O,N)-CH3(CO)(NH)(N=C(CH3)(OCH=CH2))]Cl [23]Cl, presumably through insertion of ethylene into a [Rh]-O bond.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
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) | 0.001 | 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".