Synthesis and Characterization of RuH<sub>2</sub>(H<sub>2</sub>)<sub>2</sub>(P<sup>i</sup>Pr<sub>3</sub>)<sub>2</sub> and Related Chemistry. Evidence for a Bis(dihydrogen) Structure
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Bibliographic record
Abstract
The complex RuH 2 (H 2 ) 2 (P i Pr 3 ) 2 ( 1 ) was prepared by the protonation of [K(18-crown-6)][RuH 5 (P i Pr 3 ) 2 ] with 1,3-benzenedimethanol. The observation of H−H and M−H vibrations, short T 1 (min) values of the hydride resonance, the octahedral geometry of the disordered single-crystal X-ray structure of 1, and large averaged H−D coupling constants for RuH x D 6 - x (P i Pr 3 ) 2 provide evidence for two dihydrogen and two hydride ligands. Under an atmosphere of N 2, complex 1 readily forms an equilibrium mixture of the dinitrogen complexes RuH 2 (N 2 ) 2 (P i Pr 3 ) 2 ( 2 ) and {RuH 2 (N 2 )(P i Pr 3 ) 2 } 2 (μ-N 2 ) ( 3 ), which readily reverts to 1 under an atmosphere of H 2 . Slow evaporation of a pentane solution of 1 under an atmosphere of N 2 gas resulted in the isolation of colorless crystals of 3 . Complex 1 is very unstable with respect to loss of H 2 and forms the trihydride-bridged classical polyhydride dimer (P i Pr 3 ) 2 (H)Ru(μ-H) 3 Ru(H) 2 (P i Pr 3 ) 2 ( 4 ) under an argon atmosphere or under vacuum at room temperature. Exposure of a solution of 4 to H 2 gas results in the gradual regeneration of 1 . Similarly, the known bis(dihydrogen) complex RuH 2 (H 2 ) 2 (PCy 3 ) 2 ( 5 ) was also prepared by protonation of [K(18-crown-6)][RuH 5 (PCy 3 ) 2 ]. An attempt to isolate RuH 2 (H 2 ) 2 (PPh 3 ) 2 ( 6 ) by protonation of K[RuH 5 (PPh 3 ) 2 ] resulted in the in situ formation of an equilibrium mixture of the bis(dihydrogen) complex 6 and the nonclassical dimer (PPh 3 ) 2 (H)Ru(μ-H) 3 Ru(H 2 )(PPh 3 ) 2 ( 7 ). The crystal structures of 3, 4, and 7 are reported.
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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 | 0.002 | 0.002 |
| Meta-epidemiology (narrow) | 0.003 | 0.004 |
| Meta-epidemiology (broad) | 0.004 | 0.002 |
| Bibliometrics | 0.001 | 0.004 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.001 | 0.002 |
| Open science | 0.002 | 0.001 |
| Research integrity | 0.003 | 0.002 |
| 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 it