Synthesis, Characterization, and Electrochemical Studies on [1.1]Ferrocenophanes Containing Aluminum, Gallium, and Indium
Bibliographic record
Abstract
The synthesis, characterization, structure, and electrochemistry of [1.1]ferrocenophanes, bridged by the heavier group 13 elements aluminum (1a), gallium (1b), and indium (1c), are described and discussed. Compounds 1a-c have been synthesized from dilithioferrocene and intramolecularly coordinated group 13 element dihalides Ar'EX(2) (Ar' = 2-(Me(2)NCH(2))C(6)H(4); EX(2) = AlCl(2), GaCl(2), InI(2)). Although the synthesis and characterization of 1a by single-crystal X-ray analysis has been described recently (Braunschweig, H.; Burschka, C.; Clentsmith, G. K. B.; Kupfer, T.; Radacki, K. Inorg. Chem. 2005, 44, 4906), compounds 1b and 1c are described for the first time. The galla (1b) and the inda (1c) [1.1]ferrocenophane have been characterized by single-crystal X-ray determination [1b: C(38)H(40)Fe(2)Ga(2)N(2), monoclinic, P2(1)/c, a = 10.3467(5) Angstroms, b = 11.6311(4) Angstroms, c = 14.0747(7) Angstroms, beta = 105.931(2) degrees, Z = 2; 1c: C(38)H(40)Fe(2)In(2)N(2), monoclinic, P2(1)/c, a = 10.5522(7) Angstroms, b = 11.8476(8) Angstroms, c = 13.9855(9) Angstroms, beta = 104.990(3) degrees, Z = 2]. All three compounds 1a-c are anti conformers with trans orientations of the two donating NMe(2) groups. For the [1.1]ferrocenophane 1a, an unprecedented fully reversible two-electron redox process was observed by cyclic voltammetry, whereas the corresponding Ga and In species exhibit a more conventional stepwise redox chemistry. According to the Robin-Day classification, 1a is a class I and 1b and 1c are class II species. In addition to the reversible processes, compound 1a shows an irreversible oxidation at higher voltages accompanied by adsorption processes. The irreversible adsorption process was investigated with an electrochemical quartz crystal microbalance (EQCM).
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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 | 0.000 | 0.001 |
| 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 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".