Ruthenium Complexes Stabilized by Bidentate Enamido-Phosphine Ligands: Aspects of Cooperative H<sub>2</sub> Activation
Bibliographic record
Abstract
Four bidentate, hybrid ligands ((R)(NP)(R')H) featuring imine-nitrogen and alkyl-phosphine donors linked by a cyclopentyl ring were synthesized. The ortho position of the aryl group attached to nitrogen is varied such that R is Me or Pr(i); additionally, the groups decorating phosphorus (R') are varied between Bu(t) or Pr(i). The addition of each ligand to RuHCl(PPr(i)3)2(CO) in the presence of KOBu(t) generates four enamido-phosphine complexes RuH{(R)(NP)(R')}(PPr(i)3)(CO) that were characterized by NMR spectroscopy, elemental analyses, and, in the case of R = Pr(i) and R' = Bu(t) or Pr(i), X-ray crystallography. Depending on R', the reaction of RuH{(R)(NP)(R')}(PPr(i)3)(CO) with H2 generates varying amounts of the imine-phosphine complex RuH2{(R)(NP)(R')H}(PPr(i)3)(CO). Insights into the mechanism of H2 activation by these enamido derivatives were explored using RuH{(Pr)(NP)(Pri)}(PPr(i)3)(CO), for which an intermediate was identified as the dihydrogen-dihydride complex, RuH2(H2){(Pri)(NP)(Pri)H}(PPr(i)3)(CO), on the basis of the T1,min value of 22 ms for the (1)H NMR resonance at δ -7.2 at 238 K (measured at 400 MHz). The N donor of the enamine tautomeric form of the ligand is protonated by H2 or D2 and dissociates from Ru. Tautomerization of the enamine to the imine form of the dissociated arm is involved in formation of the final product.
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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 | 0.001 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| 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 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".