Ring Opening and C−O and C−N Bond Cleavage by Transient Reduced Thorium Species
Bibliographic record
Abstract
Reduction of the tetravalent complex [{2,5-[(C 4 H 3 N)CPh 2 ] 2 [C 4 H 2 N(Me)]}ThCl 2 (THF)]·THF ( 2 ) of the tripyrrolide dianion 2,5-[(C 4 H 3 N)CPh 2 ] 2 C 4 H 2 N(Me) afforded different products depending on the reaction conditions. In every case, the reaction proceeded via the initial formation of a reduced species, as indicated by the very rapid formation of a dark red color followed by slow and complete discoloration. In the case of the reduction in toluene, the complexes ({2,5-[(C 4 H 3 N)CPh 2 ] 2 [C 4 H 2 N]} 2 Th[K(toluene)] 2 )·1.5(toluene) ( 3a ) and {2,5-[(C 4 H 3 N)CPh 2 ] 2 [C 4 H 2 N]} 2 Th[K(DME)] 2 ( 3b ) were obtained, depending on the crystallization solvent (toluene versus DME). In both cases, the products arose from a loss of the methyl group attached to the central pyrrole ring N atom. When the reduction was carried out in DME as a solvent, the complex {[{2,5-[(C 4 H 3 N)CPh 2 ] 2 [C 4 H 2 N(Me)]}Th(OMe)] 2 ( m -OC 2 H 4 OMe) 2 }· 0.75(hexane) ( 5 ) was isolated. This species is derived from two different pathways of C−O cleavage of the DME solvent. Reduction of {2,5-[(C 4 H 3 N)CPh 2 ] 2 [C 4 H 2 N(Me)]}ThCl{(C 4 H 3 N)CPh 2 [C 4 H 3 N(Me)]} ( 6 ), containing both the monoalkylated tripyrrolide and dipyrrolide ligands, afforded instead pyrrolide ring opening and formation of [({2,5-[(C 4 H 3 N)CPh 2 ] 2 [C 4 H 2 N(Me)]}Th[(C 4 H 3 N)CPh 2 (C CHCH CHNMe)]) 2 ( m -K)][K(DME) 4 ]·2(hexane) ( 7 ).
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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 | 0.000 |
| 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) | 0.000 | 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".