Approaches to alkane functionalization with Tp′Pt and (nacnac)Pt reagents
Bibliographic record
Abstract
In this perspective article we give an overview of our studies of C–H activation with platinum over the past decade. The scorpionate ligand Tp′ (Tp′ = hydrotris(3,5-dimethylpyrazolyl)borate) has exhibited the ability to stabilize both Pt(IV) and Pt(II) complexes due to flexibility between κ3 and κ2 binding modes. Control of the Tp′ coordination mode and Pt oxidation state is tightly coupled with acid/base chemistry. This ability allowed us to model a spectrum of intermediates in C–H activation reactions, including Pt(IV) alkyl hydrides, five-coordinate Pt(IV) silyl hydrides, and Pt(II) benzene complexes. We have been able to observe sturdy Pt(II) benzene complexes and probe their equilibria with the respective C–H activated Pt(IV) species in the presence of an added ligand. We have also taken steps toward functionalizing hydrocarbons with Tp′Pt by dehydrogenation of alkanes and by arylation of olefins. We have recently turned to bidentate nacnac (nacnac = N-phenyl-β-enamineimine) ligands in the hopes of catalytically functionalizing hydrocarbons.Key words: C–H activation, reductive elimination, Tp′Pt, five-coordinate, β-diiminate.
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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 | 0.001 |
| Insufficient payload (model declined to judge) | 0.002 | 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".