The pivotal role of electronics in preferred alkene over alkyne Ni–carboryne insertions and absolute regioselectivities
Bibliographic record
Abstract
The in situ formation mechanisms of active Ni-carboryne species (COM1) and subsequent alkene/alkyne Ni-C bond insertion priorities, as well as relevant cycloaddition regioselectivities and kinetics, were investigated using the IDSCRF-B3LYP density functional theory (DFT) method, and all atoms were equitably treated at the DGDZVP level. The results reveal the o-carborane species to be energetically hedged into a four-step path (barrier heights 5.3, 19.7, 18.4 and 0.3 kcal mol-1, respectively) prior to being transferred into the active Ni-carboryne species (COM1) with the assistance of nBuLi and NiCl2(PPh3)2 at room temperature. In direct agreement with empirical trends, alkene insertion into Ni-C bonds on COM1 is exclusively favoured over the competing alkyne insertion. Electronic structure analyses of the corresponding transition structures showed that the preference of alkenes to alkynes is due to different bonding characteristics during this insertion process, namely, back donation for alkenes but donation for alkyne insertion, as evidenced by molecular graphics and NBO charge distributions. Subsequent alkyne additions (i.e. post alkene insertion) arise as the rate-determining step (RDS) for each of the five different reactions (a-e) explored. The solution free-energy barriers of these RDSs (30.5-38.5 kcal mol-1) were in quantitative agreement with their corresponding experimental yields, evidencing the reliability of the DFT results to reproduce chemical phenomena and energetic trends in real Ni-catalysed carboryne-alkene/alkyne cycloadditions.
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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) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.001 | 0.001 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.003 | 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".