Physical insights into mechanistic processes in organometallic chemistry: an introduction
Bibliographic record
Abstract
The challenges of research into the mechanisms of 4d versus 3d late transition metal homogeneous catalysts is considered here, particularly catalysts containing hydrides. Included are case studies of C-H bond activation as studied in a collaboration of the Weller and McIndoe groups where a ruthenium (4d) hydride intermediate is detected using ESI-MS analysis of the catalytic mixture, and as studied in a collaboration of the Thomas and Neidig groups where a hydride transfer step involving low valent iron (3d) catalytic species is investigated using low temperature methods including Mössbauer spectroscopy. In the asymmetric hydrogenation of olefins, mechanisms are considered for rhodium (4d) vs. the newly discovered cobalt (3d) metal catalysts from the Shevlin and Chirik groups. The Hintermair group has recently described a study of a Noyori ruthenium catalyst for the ATH of acetophenone in basic 2-PrOH using a variety of flow sampling methods including flow NMR. This mechanism is highlighted along with our iron hydride work in homogeneous asymmetric hydrogenation.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.001 | 0.001 |
| Meta-epidemiology (narrow) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.001 |
| Bibliometrics | 0.001 | 0.001 |
| Science and technology studies | 0.001 | 0.004 |
| Scholarly communication | 0.002 | 0.006 |
| Open science | 0.002 | 0.001 |
| Research integrity | 0.002 | 0.004 |
| Insufficient payload (model declined to judge) | 0.006 | 0.002 |
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 source (direct Gemma or distilled Codex), 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".