Probing the Dynamics and Reactivity of a Stereochemically Nonrigid Cp*Ru(H)(κ<sup>2</sup>-<i>P</i>,<i>C</i>arbene) Complex
Bibliographic record
Abstract
The ability of the coordinatively saturated, 18-electron Cp*(H)Ru═CHR complex 1 to serve as a masked source of the coordinatively unsaturated Cp*Ru-CH 2 R species 2 via reversible α-hydride elimination was surveyed. The rate constant for this dynamic process (300 K, C 6 D 6 ) was measured to be 59 ± 1 s −1, on the basis of data obtained from selective inversion NMR experiments. Exposure of 1 to an atmosphere of CO or to an equivalent of either PMe 3 or PH 2 Ph afforded the corresponding 2·L adduct (L = CO, 98%; PMe 3, 93%; PH 2 Ph, 67%). Treatment of 1 with Ph 2 SiH 2, PhSiH 3, Ph 2 SiClH, or PhSiClH 2 afforded the corresponding net Si−H addition product, 3a − d (82−94%); an NMR spectroscopic investigation of the analogous reaction of 1 with Ph 2 SiD 2 provided evidence in support of a reaction mechanism involving previously undocumented Si−H addition across the Ru═C unit in 1 in the formation of 3a . Addition of Jutzi’s acid (H(OEt 2 ) 2 B(C 6 F 5 ) 4 ) to 1 resulted in the quantitative formation of 4 (the N- C - H cyclometalated variant of [Cp*Ru(κ 2 -2- N Me 2 -3- P i Pr 2 -indene)] + B(C 6 F 5 ) 4 − ). In monitoring the progress of the reaction of 1 with excess catecholborane (HBcat), evidence for the formation of the B−H addition product 5i was obtained en route to the isolable (Bcat)Ru═C species ( 5, 54%). Conversely, no intermediates were observed in the reaction of 1 with mesitylborane (MesBH 2 ) leading to the Cp*Ru(P,N) complex 6 (81%), which features a tethered borane fragment and a Ru−H−B bridge. Crystallographic characterization data are provided for 2·PMe 3, 3a, 3b, 3d, 5, and 6 .
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
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) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| 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 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".