Methylene-to-Acetyl Conversion in Heterobinuclear Rh/Os Complexes: Models for Oxygenate Formation by Bimetallic Fischer−Tropsch Catalysts
Bibliographic record
Abstract
Protonation of the methylene-bridged complex [RhOs(CO) 3 (μ-CH 2 )(μ-CO)(dppm) 2 ][CF 3 SO 3 ] with triflic acid at −80 °C yields the methyl complex [RhOs(CO) 4 (μ-CH 3 )(dppm) 2 ][CF 3 SO 3 ] 2 ( 1 ) in which the methyl group is primarily bound to Os while involved in an agostic interaction with Rh. Warming this species to −20 °C results in methyl migration to a terminal site on Rh, yielding [RhOs(CH 3 )(CO) 2 (μ-CO) 2 (dppm) 2 ][CF 3 SO 3 ] 2 ( 2 ), and subsequent warming to ambient temperature results in migratory insertion to yield the acetyl-bridged [RhOs(CF 3 SO 3 )(CO) 2 (μ-C(CH 3 )O)(μ-CO)(dppm) 2 ][CF 3 SO 3 ] ( 3 ). Replacement of the coordinated triflate anion in 3 by CO and PMe 3 occurs at low temperature to give [RhOs(L)(CO) 2 (μ-C(CH 3 )O)(μ-CO)(dppm) 2 ][CF 3 SO 3 ] 2 (L = CO ( 4 ), PMe 3 ( 5a )). Warming the PMe 3 adduct results in transformation of the acetyl group, which is C-bound to Rh in 5a, to a group that is C-bound to Os in 5b . One carbonyl in 3 is labile and is readily lost, yielding [RhOs(CF 3 SO 3 )(CO) 2 (μ-C(CH 3 )O)(dppm) 2 ][CF 3 SO 3 ] ( 6 ). Attempts to obtain the above methyl or acetyl species by reaction of the hydride-bridged species [RhOs(X)(CO) 3 (μ-H)(μ-CO)(dppm) 2 ][X] (X = CF 3 SO 3 ( 7a ), BF 4 ( 7b )) with diazomethane were unsuccessful.
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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 | 0.001 | 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 | 0.001 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.007 | 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".