Diamido-Ether Actinide Complexes as Catalysts for the Intramolecular Hydroamination of Aminoalkenes
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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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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 it