Simultaneous Observation of Doubly and Triply Chloride Bridged Isomers of an Electron-Rich Ruthenium Dimer: Role of Dimer Geometry in Determining Reactivity
Bibliographic record
Abstract
High-yield routes to the dimeric monocarbonyl complexes [RuCl 2 (PP)(CO)] 2 ( 3; PP = dcypb, 1,4-bis(dicyclohexylphosphino)butane) are established via (a) decarbonylation of mononuclear RuCl 2 (PP)(CO) 2 ( 4 ), (b) one-pot carbonylation−decarbonylation of RuCl(PP)(μ-Cl) 3 Ru(PP)(N 2 ) ( 1 ), and, most conveniently, (c) phosphine exchange of RuCl 2 (PPh 3 ) 3 with dcypb, followed by a carbonylation−decarbonylation sequence as in (b), all three steps being carried out in a one-pot procedure. One or three isomers of 3 can be observed by NMR analysis, depending on the solvent medium. A mixture of [RuCl(PP)(CO)] 2 (μ-Cl) 2 (transoid, 3a; cisoid, 3b ) and ionic {[Ru(PP)(CO)] 2 (μ-Cl) 3 }Cl ( 3c ) is present in benzene, chlorobenzene, or THF. In CH 2 Cl 2 or CDCl 3, only 3c is observed. This represents the first Ru 2 X 4 L 4 system (L = L, L‘) in which three of the possible edge-bridging and face-bridging isomers can be simultaneously observed and in which their ratio can be manipulated. Reactivity studies indicate that the face-sharing isomer 3c is considerably more stable than its edge-sharing isomers. Transformations of 3 are significantly accelerated by introduction of a donor solvent (methanol, THF). Product identities were established by 1 H, 13 C, and 31 P NMR and IR spectroscopy, by microanalysis, and by X-ray crystallography ( 3a / 3b, 3c, 4a / 4b ).
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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 | 0.001 |
| 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) | 0.000 | 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".