A Density Functional Study of S<sub>N</sub>2 Substitution at Square-Planar Platinum(II) Complexes
Bibliographic record
Abstract
The energetics and reaction path in a series of S(N)2 substitution reactions at square-planar Pt(II) complexes have been studied by the application of density functional theory (DFT). Calculated free energies show excellent correlation with their experimental counterparts, while the enthalpic and entropic contributions individually indicate the presence of weak intermolecular interactions not accounted for in the present model. The nature of the leaving ligand has been shown to be much more significant in determining the activation barrier than that of the entering ligand; it is inferred (and confirmed by analysis of individual bond energies) that the reaction is driven by the dissociation of the leaving ligand, with the entering ligand playing a more passive role. Analysis of the intrinsic reaction coordinate indicates, further, that the trans ligand plays an unexpectedly dynamic role in stabilizing the transition state due to competition between stabilization and the steric effects of the entering and leaving ligands. The cis ligands, by contrast, are shown to move only slightly through the course of the reaction.
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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) | 0.001 | 0.001 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.001 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.001 | 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".