C(sp<sup>3</sup>)–C(sp<sup>3</sup>) Reductive Elimination from (Phenoxyimine)Cobalt(III)(CH<sub>3</sub>)<sub>2</sub>(PMe<sub>3</sub>)<sub>2</sub> Complexes
Bibliographic record
Abstract
A series of six-coordinate, idealized octahedral phenoxyimine (FI)–cobalt(III) dimethyl bis(trimethylphosphine) complexes was synthesized and characterized by NMR spectroscopy and single-crystal X-ray diffraction. The thermal stability of the parent Ph-FI complex was evaluated at 60 °C in benzene- d 6, and a 13(1):1 ratio of ethane to methane was observed. The major detectable cobalt product of this reaction was the bis(chelate) cobalt derivative (Ph-FI) 2 Co formed by disproportionation of the (FI)cobalt(I) product following ethane reductive elimination. Addition of excess PMe 3 inhibited C(sp 3 )–C(sp 3 ) reductive elimination, consistent with phosphine dissociation preceding C–C bond formation from a five-coordinate (FI)cobalt(III) dimethyl intermediate. The reductive elimination of substituted (R-FI)cobalt(III) dimethyl bis(trimethylphosphine) compounds was evaluated in acetonitrile- d 3, where ligands bearing electron-donating aniline substituents underwent reductive elimination the fastest and electron-withdrawing substituents the slowest. These data support a buildup of positive charge in the rate-limiting step, consistent with the formation of a more electropositive five-coordinate cobalt center prior to rate-limiting C–C reductive elimination. Attempted synthesis of a cobalt(III) dimethyl complex bearing a sterically hindered FI ligand with a tert -butyl substituent ortho to the phenol led exclusively to the corresponding bis(chelate) cobalt derivative, whose formation was rationalized by steric destabilization of pre–reductive elimination intermediates.
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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 | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| 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) | 0.001 | 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 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".