Infrared Study of the Class II/Class III Boundary in Mixed-Valence Dinuclear Ruthenium Complexes
Bibliographic record
Abstract
The cyanamide stretching frequencies of the mixed-valence complexes [{Ru(NH 3 ) 5 } 2 (μ-L)] 3+, trans, trans -[{Ru(NH 3 ) 4 (py)} 2 (μ-L)] 3+ (py = pyridine), and mer, mer -[{Ru(NH 3 ) 3 (bpy)} 2 (μ-L)] 3+ (bpy = 2,2‘-bipyridine), where L is the 1,4-dicyanamidobenzene dianion and its substituted derivatives in nitromethane, acetonitrile, and dimethyl sulfoxide, were examined to determine the effects of inner- and outer-sphere perturbation on electron delocalization. The solvent-dependent infrared spectra of [{Ru(NH 3 ) 5 } 2 (μ-Me 2 dicyd)] 3+, where Me 2 dicyd 2 - is the 2,5-dimethyl-1,4-dicyanamidobenzene dianion, yield evidence for a transformation from localized to delocalized behavior and confirm the effect of outer-sphere perturbation on the mixed-valence state. The IR spectrum of trans, trans -[{Ru(NH 3 ) 4 (py)} 2 (μ-Me 2 dicyd)] 3+ in acetonitrile is consistent with Class III properties, and this complex's properties can be regarded as benchmarks for delocalization in our systems. It is shown that this complex obeys the general condition for delocalization in symmetric mixed-valence complexes, 2 H = λ, and possesses an experimental free energy of resonance exchange Δ G r ‘ = 1250 cm - 1 and resonance exchange integral H = 3740 cm - 1 .
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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 | 0.000 |
| 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 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".