Diamido-Ether Actinide Complexes as Catalysts for the Intramolecular Hydroamination of Aminoalkenes
Bibliographic record
Abstract
The synthesis and characterization of a series of new diamido-thorium(IV) and diamido-uranium(IV) halide and alkyl complexes supported by three different diamido-ether ligands are reported. Reaction of ThCl 4 ·2DME with [(RNSiMe 2 ) 2 O]Li 2 ([ R NON]Li 2 ) in DME when R = t Bu gives [ t Bu NON]ThCl 5 Li 3 ·DME ( 1 ), when R = i Pr 2 Ph in diethyl ether [ i Pr 2 Ph NON]ThCl 3 Li·DME ( 3 ) is prepared. Reaction of UCl 4 with [ i Pr 2 Ph NON]Li 2 in diethyl ether gives {[ i Pr 2 Ph NON]UCl 2 } 2 ( 4 ). Reaction of ThCl 4 ·2DME with Li 2 [( i Pr 2 PhNCH 2 CH 2 ) 2 O] ([ i Pr 2 Ph NCOCN]Li 2 ) in DME gives [ i Pr 2 Ph NCOCN]ThCl 2 ·DME ( 5 ). The addition of 2 equiv of LiCH 2 SiMe 3 to 1 and 5 resulted in salt- and base-free [ t Bu NON]Th(CH 2 SiMe 3 ) 2 ( 7 ) and [ i Pr 2 Ph NCOCN]Th(CH 2 SiMe 3 ) 2 ( 9 ), respectively. Complexes 1, 3, 4, 7, and 9, as well as previously reported {[ t Bu NON]UCl 2 } 2 ( 2 ), [ t Bu NON]U(CH 2 SiMe 3 ) 2 ( 6 ), and [ i Pr 2 Ph NCOCN]U(CH 2 SiMe 3 ) 2 ( 8 ) were examined as catalysts for the intramolecular hydroamination of a series of aminoalkenes. Complexes 6 – 9 were shown to facilitate the formation of 2-methyl-4,4-diphenylpyrrolidine from 2,2-diphenyl-1-amino-4-pentene at room temperature. For 9, this reaction occurs in less than 15 min, while for other dialkyls 6 – 8, the reaction takes less than 2 h. Dihalides 1 and 2 facilitated the same reaction at 60 °C in 4 h, while 3 and 4 showed no activity under the same conditions. Dialkyl complexes 7 – 9 were examined for further reactivity with different substrates. The uranium dialkyl 8 was more active than 7 and 9 for the cyclization of 2,2-diphenyl-1-amino-5-hexene and 2,2-diphenyl-1-amino-6-heptene, as well as more active in the cyclization of N -methyl-2,2-diphenyl-1-amino-4-pentene, a secondary amine. All three dialkyls became less active when the steric bulk of the gem -substituents was decreased from diphenyl to cyclopentyl; reactivity further decreased when the steric bulk of the substituents was decreased further to hydrogen.
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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) | 0.001 | 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".