Ruthenium Cyclopentadienyl Aryldiazenido Complexes. Synthesis of [Cp‘Ru(PR<sub>3</sub>)<sub>2</sub>(N<sub>2</sub>C<sub>6</sub>H<sub>4</sub>OMe)][BF<sub>4</sub>]<sub>2</sub>and [Cp‘RuCl(PPh<sub>3</sub>)(N<sub>2</sub>C<sub>6</sub>H<sub>4</sub>OMe)][BF<sub>4</sub>] (Cp‘ = Cp, Cp*) and X-ray Crystal Structure of [CpRu(PPh<sub>3</sub>)<sub>2</sub>(N<sub>2</sub>C<sub>6</sub>H<sub>4</sub>OMe)][BF<sub>4</sub>]<sub>2</sub>, an Aryldiazenido Complex with a Large N−N−C(aryl) Angle and Near-Linear Ru−N−N−C(aryl) Skeleton
Bibliographic record
Abstract
The neutral ruthenium complexes Cp‘Ru(PR 3 ) 2 Cl [Cp‘ = Cp, PR 3 = PPh 3, PMe 3, or 1/2 dppe; Cp‘ = Cp*, PR 3 = PMe 3 ] react with [ p -MeOC 6 H 4 N 2 ][BF 4 ] in acetone to give new cyclopentadienyl ruthenium aryldiazenido dicationic complexes [Cp‘Ru(PR 3 ) 2 (N 2 C 6 H 4 OMe)][BF 4 ] 2 [Cp‘ = Cp, PR 3 = PPh 3 ( 1 ), PMe 3 ( 2 ), or 1/2 dppe ( 3 ); Cp‘ = Cp*, PR 3 = PMe 3 ( 4 )] in good yields. The dicationic complexes 1 − 3 may also be conveniently isolated in better yield by treatment of the acetonitrile ruthenium complexes [CpRu(PR 3 ) 2 (NCMe)][BF 4 ] with the arenediazonium salt. When the reaction of Cp‘Ru(PPh 3 ) 2 Cl (Cp‘ = Cp or Cp*) with [ p -MeOC 6 H 4 N 2 ][BF 4 ] is carried out in toluene, the product is instead the cyclopentadienyl ruthenium aryldiazenido monocationic complex [Cp‘RuCl(PPh 3 )(N 2 C 6 H 4 OMe)][BF 4 ] [Cp‘ = Cp ( 5 ) or Cp* ( 6 )]. Further, if the reaction of Cp*Ru(PPh 3 ) 2 Cl with diazonium salt is carried out in acetone, the binuclear complex [Cp*RuCl(N 2 C 6 H 4 OMe)] 2 [Cl] 2 ( 7 ) can be isolated in low yield in addition to 6 . All new complexes 1 − 7 were fully characterized by NMR, FT-IR, and mass spectroscopies. The structure of [CpRu(PPh 3 ) 2 (N 2 C 6 H 4 OMe)][BF 4 ] 2 ·0.93CHCl 3 ( 1· 0.93CHCl 3 ) was determined by single-crystal X-ray diffraction. The structure exhibits a near-linear Ru−N−N−C geometry for the coordinated aryldiazenido group, with the NNC angle having a value of 159°, compared to the “sp 2 ” value of approximately 120° commonly exhibited by other “singly bent” aryldiazenido complexes. On the basis of NMR spectroscopic data, 1 reacts with NaBH 4 at low temperature to give an arylhydrazido(2−) complex [CpRu(PPh 3 ) 2 {NN(H)C 6 H 4 OMe}][BF 4 ], which readily converts to the corresponding aryldiazene complex [CpRu(PPh 3 ) 2 (NH NC 6 H 4 OMe)][BF 4 ] by a hydrogen shift; at room temperature, the only product is the hydrido complex CpRuH(PPh 3 ) 2 .
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How this classification was reachedexpand
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 | 0.023 | 0.011 |
| Meta-epidemiology (narrow) | 0.048 | 0.054 |
| Meta-epidemiology (broad) | 0.048 | 0.024 |
| Bibliometrics | 0.025 | 0.045 |
| Science and technology studies | 0.021 | 0.028 |
| Scholarly communication | 0.017 | 0.024 |
| Open science | 0.031 | 0.022 |
| Research integrity | 0.027 | 0.036 |
| Insufficient payload (model declined to judge) | 0.001 | 0.009 |
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; both teacher heads agree on what is shown here.
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".