Tuning Energetics of 2 e<sup>−</sup>/2H<sup>+</sup> PCET Properties with Model Ru‐bisamido Complexes
Bibliographic record
Abstract
Abstract Most redox processes that break/form bonds involve net 2e − changes, and many are coupled to protons. Yet most proton‐coupled electron transfer (PCET) studies focus on 1e − /1H + reactions. Reported here is a family of molecular models that undergo tunable 2e − /2H + redox changes. Complexes [(X 2 bpy)Ru II (en*) 2 ](PF 6 ) 2 and [(X 2 bpy)Ru IV (en*‐H) 2 ](PF 6 ) 2 have been synthesized with bpy=2,2’‐bipyridine with 4,4’‐subtitutions X=−NMe 2 , −OMe, −Me, −H, −CF 3 ; and en*=2,3‐dimethyl‐2,3‐butanediamine. They have been characterized by IR, UV‐vis, and NMR spectroscopies, XRD, electrochemistry, mass spectrometry, DFT and (TD)DFT computations. The introduction of electron‐withdrawing and donating groups at the 4,4’‐position of the bpy ligand affects the complexes’ redox potentials, p K a ’s, and Bond Dissociation Free Energies (BDFEs) of the N−H bonds in the en* ligands. The average BDFEs for the overall 2e − /2H + PCET span over 5 kcal/mol. Notably, these complexes all show marked potential inversion over an extended range, Δp K a >25 units and Δ E 0 >1.4 V. Potential inversion remains despite the electronic influence of bpy's substitutions which regulate N−H properties several bonds apart by trans‐effect over dπ‐molecular orbitals at the Ru center. The experimental and computational results presented in this work support the presence of strong coupling between electrons and protons, for modelling insights of 2e − /2H + transfer reactivity.
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How this classification was reachedexpand
Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.001 | 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 | 0.001 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| 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 teacher head, 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".