Kinetics and Magnetism of Phosphane Diadducts of Diruthenium(II,III) Tetraacetate
Bibliographic record
Abstract
Abstract The kinetic parameters for the axial‐ligand‐substitution reactions of [Ru 2 (μ‐O 2 CCH 3 ) 4 (MeCN) 2 ] + in acetonitrile (MeCN) with PCy 3 and PCy 2 Ph (Cy = cyclohexyl and Ph = phenyl) were investigated under pseudo first‐order conditions of excess phosphane. The rate‐determining formation of [Ru 2 (μ‐O 2 CCH 3 ) 4 (MeCN)(PCy 2 R] + appears independent of the nature of the incoming phosphane with an average k 1 (25.0 °C) = (1.25 ± 0.06) × 10 3 M –1 s –1 . A dissociatively activated mechanism is proposed for substitution of the axially coordinated acetonitrile, and the rate parameters are compared to earlier measurements carried out on [Rh 2 (μ‐O 2 CCH 3 ) 4 (MeCN) 2 ]. Variable‐temperature magnetic susceptibility measurements were carried out on the two phosphane diadducts, [Ru 2 (μ‐O 2 CCH 3 ) 4 (PCy 3 ) 2 ]PF 6 , ( 1 ) and [Ru 2 (μ‐O 2 CCH 3 ) 4 (PCy 2 Ph) 2 ]PF 6 ( 2 ), and showed behaviour unique to a Boltzmann distribution of states over the temperature range 2–300 K. To support the magnetic measurements, the single‐crystal X‐ray structure of 1 was redetermined at various temperatures down to –150 °C and showed a distinct decrease in the Ru–Ru bond length with decreasing temperature, consistent with a σ 2 π 4 δ 2 π* 3 configuration at low temperature (ground state) and a σ 2 π 4 δ 2 π* 2 δ* 1 configuration at room temp. In addition, the structure redeterminations of 1 were better resolved than the earlier reported structure and also corrected a minor error in that the molecule of solvation was found to be 1,2‐dichloroethane instead of dichloromethane. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
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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 | 0.001 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 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) | 0.010 | 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".