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 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 | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.003 | 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".