A Stable Silylene in a Reactive Environment: Synthesis, Reactivity, and Silicon Extrusion Chemistry of a Coordinatively Unsaturated Ruthenium Silylene Complex Containing Chloride and η<sup>3</sup>-P−C−P Ligands
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Bibliographic record
Abstract
Reaction of [(dcypb)ClRu(μ-Cl) 3 Ru(dcypb)(N 2 )] ( 1 ) with 4 equiv of the stable silylene 1,3-di- tert -butyl-1,3,2-diazasilol-2-ylidene (SiL N 2 ) yields coordinatively unsaturated RuCl(η 3 -dcypb)(SiL N 2 ) ( 2 ). Complex 2 is a rare example of a trans-spanning diphosphine complex, this geometry resulting from an unprecedented attack of the metal on the tetramethylene ligand backbone. X-ray and solid-state 31 P NMR and IR analysis reveal an agostic interaction between the metal and a silylene Bu t group. In solution, this interaction is observed only at low temperature. Reaction of 2 with H 2 containing trace H 2 O yields siloxane dimer [L N 2 Si(H)] 2 O 3 and the ruthenium hydride−H 2 adduct [(dcypb)(H)Ru(μ-Cl) 2 (μ-H)Ru(dcypb)(H 2 )] ( 4 ). Attempts to isolate 4 resulted in serendipitous crystallization of decomposition product 5, [(dcypb)(H)Ru(μ-Cl) 3 Ru(dcypb)(N 2 )]. X-ray analysis of 5 revealed a structure closely analogous to that of 4, in which bridging hydride is replaced by chloride, and η 2 -H 2 by η 2 -N 2 . Displacement of silylene from 2 is facile: treatment with 1 atm of CO affords free SiL N 2, accompanied by RuCl(η 3 -dcypb)(CO) 2 as a mixture of three isomers ( 6 − 8 ).
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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 | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.001 | 0.001 |
| 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 | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.011 | 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