Regioselective C–H Activation of Cyclometalated Bis-Tridentate Ruthenium Complexes
Bibliographic record
Abstract
A series of bis - tridentate Ru(II) complexes consisting of trimethyl-4,4′,4″-tricarboxylate-2,2′:6′,2″-terpyridine (Me 3 tctpy) and derivatized 6-phenyl-2,2′-bipyridine (pbpy) ligands are reported. Each complex is attached to a terminal triphenylamine (TPA) substituent at the central ring of pbpy through a thiophene bridge to benefit light absorption, while the anionic ring of pbpy is functionalized with substituents to modulate the metal-based redox potential. The cyclometalation step was found to favor the isomer where the electron-donating groups (EDGs; i.e., −OEt, −SEt) are situated ortho to the organometallic bond rather than the sterically favored para position, while the para isomer is formed in exclusivity when electron-withdrawing groups (e.g., −CF 3 ) are installed on the anionic ring. Moreover, the distribution of the isomeric products is affected by the identity of the chalcogen: ortho: para = 1:0 and 3:1 where EDG = −OEt and −SEt, respectively. Because our molecular scaffold rules out certain cyclometalation pathways (e.g., oxidative addition, agostic interactions, σ-bond metathesis), we are able to experimentally establish that the observed regioselectivity is in accordance with an electrophilic metalation where the relative stabilities of the products and carbanionic intermediates govern the ratio of the isomers formed.
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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 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| 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) | 0.014 | 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".