Synthesis and reactivity of ruthenium tridentate bis-phosphinite ligand complexes
Bibliographic record
Abstract
The tridentate ligands E(CH2CH2OPiPr2)2 (E = NH 1, E = S 2) were employed in the synthesis of a number of ruthenium complexes. Reaction of these ligands with (Ph3P)3RuCl2 afforded the dimers [Ru(HN(CH2CH2OPiPr2)2)Cl(μ-Cl)]2 (3) and [(Ru(E(CH2CH2OPiPr2)2))2(μ-Cl)3][X] (E = NH, X = PF64, E = S, X = Cl 5), respectively. Using (Ph3P)3RuHCl in reactions with 1 gave Ru(NH(CH2CH2OPiPr2)2)(PPh3)HCl (6) while addition of pyridine and 2, gave Ru(S(CH2CH2OPiPr2)2)(py)HCl (7). Treatment of 6 or 7 with NaBPh4 resulted in the formation of the η(6)-arene complexes RuH(E(CH2CH2OPiPr2)2)2(η(6)-C6H5BPh3) (E = NH 8, E = S 9) while reactions with K[B(C6F5)4] gave the salts [RuH(E(CH2CH2OPiPr2)2)(L)][B(C6F5)4] (E = NH, L = PPh310, E = S, L = py 12). Compounds 6 and 7 react with CO giving RuH(HN(CH2CH2OPiPr2)2)(CO)Cl (15) and [RuH(S(CH2CH2OPiPr2)2(py)(CO)]Cl (16) respectively, while reaction of 6, 10 or 12 with dihydrogen gave RuH(HN(CH2CH2OPiPr2)2)(H2)Cl (18) and RuH(E(CH2CH2OPiPr2)2)(L)(H2)][B(C6F5)4] (E = NH, L = PPh319, E = S, L = py 20). The complexes 4-12, 15 and 16 are shown to catalyze the dehydrogenation of HMe2NBH3.
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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) | 0.000 | 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) | 0.002 | 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".