Anionic Phosphinimine-Chelate Complexes of Rhodium and Iridium: Steric and Electronic Influences on Oxidative Addition of CH<sub>2</sub>Cl<sub>2</sub>
Bibliographic record
Abstract
The phosphinimines Ph 3 PNR (R = Ph 1, 2,6-Me 2 C 6 H 3 2, 3,5-Me 2 C 6 H 3 3, 2,6- i- Pr 2 C 6 H 3 4 ) were prepared and used to generate the species of the form [Li( o -C 6 H 4 PPh 2 NR)] 2 ·Et 2 O (R = Ph 5, 2,6-Me 2 C 6 H 3 6, 3,5-Me 2 C 6 H 3 7, 2,6- i -Pr 2 C 6 H 3 8 ). Subsequent reactions with [Rh(μ-Cl)(COD)] 2 gave the complexes Rh(COD)( o -C 6 H 4 PPh 2 NR) (R = Ph 9, 2,6-Me 2 C 6 H 3 10, 3,5-Me 2 C 6 H 3 11, 2,6- i -Pr 2 C 6 H 3 12 ). Similarly, the Ir analogue of 9 ( 13 ) was prepared using [Ir(μ-Cl)(COD)] 2 . The reaction of 9 with (CH 2 PPh 2 ) 2 afforded Rh(PPh 2 CH 2 CH 2 PPh 2 )( o -C 6 H 4 PPh 2 NPh) ( 14 ). Compound 9 was also shown to react with CH 2 Cl 2 to give two products, one of which was confirmed to be [Rh( o -C 6 H 4 PPh 2 NPh)(CH 2 - o -C 6 H 4 PPh 2 NPh)(μ-Cl) 2 Rh(COD)] ( 15 ). Similar treatment of 10 and 12 with CH 2 Cl 2 showed no reaction, while reaction of 11 with CH 2 Cl 2 gave a mixture of unidentified products. The related imidazole-phosphinimine ligands (N 2 C 3 H 3 )PPh 2 NR (R = Ph 18, 2,6-Me 2 C 6 H 3 19 ) were also prepared. These ligands react with NaH to give the corresponding Na-imidazolate-phosphinimines, 20 and 21, and subsequent reaction with [Rh(μ-Cl)(COD)] 2 gave the complexes Rh(COD)((N 2 C 3 H 2 )PPh 2 NR) (R = Ph 22, 2,6-Me 2 C 6 H 3 23 ). The compounds 22 and 23 do not react with CH 2 Cl 2 . The effects of steric and electronic modifications to the ligands on oxidative addition of C−Cl bonds are discussed. DFT calculations were performed on the model fragments [Rh((C 6 H 4 )PH 2 NH)] and [Rh((N 2 C 3 H 2 )PH 2 NH)], and the calculated atomic charges provide some insight into the reactivity of these compounds.
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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 | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.000 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.002 | 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 teacher head, 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".