Calculations on the non-classical β-hydride elimination observed in <i>trans</i>-(H)(OMe)-Ir(Ph)(PMe<sub>3</sub>)<sub>3</sub>: possible production and reaction of methyl formate
Bibliographic record
Abstract
The octahedral trans hydrido-alkoxide complex trans-(H)(OMe)-Ir(Ph)(PMe3)3 (2-OCH3) was prepared by Milstein and coworkers by addition of methanol to Ir(Ph)(PMe3)3 (1). 2-OCH3 was discovered to undergo a methanol catalyzed outer-sphere carbonyl de-insertion in which a vacant coordination site is not required. The reaction yields the octahedral trans dihydride complex trans-(H)2-Ir(Ph)(PMe3)3 (2-H) as a kinetic product along with formaldehyde derivatives reported as [CH2=O]x. We investigate the mechanism and products of this reaction using density functional theory. The de-insertion transition state has an ion-pair character leading to a high barrier in benzene continuum: ΔG ‡ = 27.9 kcal/mol. Adding one methanol molecule by H-bonding to the alkoxide of 2-OCH3 lowers the barrier to 22.7 kcal/mol. When the calculations are conducted in a methanol continuum, the barrier drops to 8.8 kcal/mol. However, the thermodynamics of de-insertion are endergonic by near 5 kcal/mol in both benzene and methanol. The calculations identify a low energy outer-sphere H/OMe metathesis pathway that transforms the formaldehyde and another 2-OCH3 molecule directly into a second 2-H complex and methyl formate. Likewise, a second H/OCH3 metathesis reaction interconverting methyl formate and 2-OCH3 into 2-H and dimethyl carbonate is computed to be exergonic and kinetically facile. These results imply that the production of methyl formate and dimethyl carbonate from 2-OCH3 is plausible in this system. The net transformation from the square planar 1 and methanol to 2-H and either methyl formate or dimethyl carbonate would represent a unique stoichiometric dehydrogenative coupling reaction taking place at room temperature by an outer-sphere mechanism.
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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 | 0.001 |
| Meta-epidemiology (narrow) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.001 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.001 | 0.000 |
| Open science | 0.001 | 0.001 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.005 | 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".