Structure and Electrochemistry of Heterobimetallic Ferrocenecarboxylatoruthenium(II) Complexes
Bibliographic record
Abstract
The mixed-valent diruthenium complexes [Ru 2 (μ-O 2 CR) 4 L 2 ](PF 6 ) (where R = CH 3, L = H 2 O or R = Fc (ferrocenyl), L = MeOH) were reacted with the three diphosphine (dpp) ligands bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe), and 1,3-bis(diphenylphosphino)propane (dppp) to yield, via a disassembly reaction, the monoruthenium(II) complexes [Ru(η 2 -O 2 CR)(dpp) 2 ](PF 6 ) (R = CH 3 and dpp = dppm ( 1 ), dpp = dppe ( 2 ), dpp = dppp ( 3 ); R = Fc and dpp = dppm ( 4 ), dpp = dppe ( 5 ), dpp = dppp ( 6 )). All six complexes were characterized by elemental analysis, IR and NMR ( 1 H and 31 P) spectroscopy, cyclic and Osteryoung square wave voltammetry, and X-ray crystallography. Complexes 4 − 6 are rare examples of structurally characterized ruthenium complexes with η 2 -bound ferrocenecarboxylate ligands, and they are unique in displaying a metal and an organometallic center. The electrochemical measurements reveal an essentially reversible ruthenium-centered redox process for complexes 2 and 3, which becomes irreversible in the presence of the ferrocenyl group in complexes 4 − 6 . The iron-centered redox process in complexes 4 − 6 is chemically reversible. The separation between these redox processes is large (>1.0 V), leading to a stable “mixed-valent” state, and increases in the potential separation of these two redox processes over the separation seen between the redox potentials of the isolated ruthenium and ferrocenecarboxylate fragments may indicate the possibility of metal−metal interactions. A mechanism for the disassembly process, exploited in the synthetic procedure, is postulated.
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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".