Comparative properties of coordinated H2 and H2S at a ruthenium(ii) centre
Bibliographic record
Abstract
Thermodynamic data for the reversible formation of cis-RuCl2(P-N)(PPh3)(η(2)-H2) () from trans-RuCl2(P-N)(PPh3) in C6D6 are determined by variable temperature (31)P{(1)H} and (1)H NMR spectroscopy; P-N = o-diphenylphosphino-N,N'-dimethylaniline. Values of ΔH° = -26 ± 4 kJ mol(-1), ΔS° = -40 ± 15 J mol(-1) K(-1), and ΔG° (at 25 °C) = -13.8 ± 0.2 kJ mol(-1) are compared with recently reported data for the corresponding H2S adduct (4a), where the exothermicity is greater by ~20 kJ mol(-1), but this is counteracted by a more unfavourable entropy change, and overall the K and ΔG° values at 25 °C are close. For loss of H2 from 2a in the solid state, whose X-ray structure is presented, ΔH° is 50 ± 3 kJ mol(-1) as measured by Differential Scanning Calorimetry. The pKa values of the coordinated H2 (~11) and H2S (~14) are estimated by reactions of 2a and 4a with proton sponge (1,8-bis(dimethylamino)naphthalene) in CD2Cl2 at 20 °C; the mono-hydrido and -mercapto products are identified in situ. A corresponding H2O adduct is not deprotonated under the same conditions. Related dihydrido, mercapto and hydroxy species are formed by in situ reactions of 1a with NaH, NaSH, and NaOH, respectively.
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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) | 0.006 | 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".