Experimental and computational studies of the macrocyclic effect of an auxiliary ligand on electron and proton transfers within ternary copper(II)-Histidine complexes
Bibliographic record
Abstract
The dissociation of [Cu(II)(L)His](*2+) complexes [L = diethylenetriamine (dien) or 1,4,7-triazacyclononane (9-aneN(3))] bears a strong resemblance to the previously reported behavior of [Cu(II)(L)GGH](*2+) complexes. We have used low-energy collision-induced dissociation experiments and density functional theory (DFT) calculations at the B3LYP/6-31+G(d) level to study the macrocyclic effect of the auxiliary ligands on the formation of His(*+) from prototypical [Cu(II)(L)His](*2+) systems. DFT revealed that the relative energy barriers of the same electron-transfer (ET) dissociation pathways of [Cu(II)(9-aneN(3))His](*2+) and [Cu(II)(dien)His](*2+) are very similar, with the ET reactions of [Cu(II)(9-aneN(3))His](*2+) leading to the generation of two distinct His(*+) species; in contrast, the proton transfer (PT) dissociation pathways of [Cu(II)(9-aneN(3))His](*2+) and [Cu(II)(dien)His](*2+) differ considerably. The PT reactions of [Cu(II)(9-aneN(3))His](*2+) are associated with substantially higher barriers (>13 kcal/mol) than those of [Cu(II)(dien)His](*2+). Thus, the sterically encumbered auxiliary 9-aneN(3) ligand facilitates ET reactions while moderating PT reactions, allowing the formation of hitherto nonobservable histidine radical cations.
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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) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.001 | 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".