Structure and Electrochemistry of Various Diruthenium(II,III) Tetrametallocenecarboxylates
Bibliographic record
Abstract
A series of mixed-valent diruthenium(II,III) tetrametallocenecarboxylates of the form Ru 2 (μ-O 2 C(X)C 5 H 4 MCp) 4 Cl, where M = Fe(II) and X = nothing ( 1 ), −CH 2 − ( 2 ), −CH 2 CH 2 − ( 3 ), −CH CH− ( 5 ), M = Ru(II) and X = nothing ( 6 ), and the corresponding dechlorinated alcohol di-adducts [Ru 2 (μ-O 2 C(X)C 5 H 4 MCp) 4 (ROH) 2 ](PF 6 ), where M = Fe(II), R = ethyl or 1-propyl, and X = nothing ( 7 ), −CH 2 − ( 8 ), −CH 2 CH 2 − ( 9 ), and −CH CH− ( 10 ), and M = Ru(II) and X = nothing ( 11 ), were synthesized and characterized. In addition, the partially substituted complex with the tentative formula Ru 2 (μ-O 2 CCH 3 ) 3 (μ-O 2 C(X)C 5 H 4 FeCp) 4 Cl, where X = −CH 2 CH 2 CH 2 − ( 4 ), was partially characterized. Complex 7 was structurally characterized previously, and the structures of complexes 10 and 11 are reported here. The complexes differ significantly in the orientation of the metallocenyl rings with respect to each other. An extension of the electrochemical studies that previously revealed evidence of ferrocenyl−ferrocenyl communication in complex 7 shows that this interaction is absent as the X group is lengthened and saturated, but a small degree of communication is still present in complex 10, which contains an unsaturated, conjugated, spacer. The trend in the ferrocenyl-based redox process for complexes 7 − 10 mimics that of the corresponding free acids. No interactions are seen in the ruthenocenyl derivative ( 11 ) due to the irreversibility of its ruthenocenyl-centered redox processes.
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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".