Substituents Effects in POP Pincer Complexes of Ruthenium
Bibliographic record
Abstract
Reactions of [RuCl 2 ( p -cymene)] 2 with ( t Bu 2 PCH 2 CH 2 ) 2 O (POP- t Bu) and ( i Pr 2 PCH 2 CH 2 ) 2 O (POP- i Pr) afforded RuCl 2 (POP- t Bu) ( 1 ) and [Ru 2 (μ-Cl) 3 (POP- i Pr) 2 ]Cl ( 2 ·Cl), respectively. The POP ligand is coordinated in a mer fashion in complex 1, whose crystal structure revealed a γ-agostic C−H···Ru interaction of one t Bu group. Spectroscopic evidence indicated that this agostic interaction is retained in 1 in solution. A related compound, [Ru(N 2 )Cl(POP- t Bu)]BPh 4 ( 4 ), which also showed agostic bonding of a t Bu group, was obtained by substitution of N 2 for Cl - in 1, in the presence of NaBPh 4 . Compound 2 ·Cl readily underwent ion exchange with LiBPh 4 or LiPF 6 to give 2 ·BPh 4 or 2 ·PF 6 salts, respectively. A crystallographic analysis of 2 ·PF 6 established a co-facial bioctahedral geometry of the [Ru 2 (μ-Cl) 3 (POP- i Pr) 2 ] + cation containing two POP ligands coordinated in a fac fashion. Reactions of 1 and 2 with H 2 afforded the dihydrogen complexes cis, trans -Ru(H 2 )Cl 2 (POP- t Bu) ( 3 ) and cis, cis -Ru(H 2 )Cl 2 (POP- i Pr) ( 5 ), respectively. The H−H bond distances are very similar in both compounds, r (H−H) = 1.0 ± 0.1 Å, based on the T 1min and J HD data and results of DFT calculations. Reaction of 2 with N 2 gave the dinitrogen complex cis, cis -Ru(N 2 )Cl 2 (POP- i Pr) ( 6 ), but solutions of 1 under a nitrogen atmosphere showed no evidence of an analogous compound. The different steric requirements of the phosphorus substituents of the POP ligands were identified as the source of the differences in the coordination properties of the POP- t Bu and POP- i Pr complexes 1 − 6 .
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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) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.031 | 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".