Synthesis of Acyclic NPNCN Systems and Metalation Reactions with Organolithium, -magnesium, and -aluminum Reagents
Bibliographic record
Abstract
The preparation of a new family of acyclic DippN(H)P(Ph)NRCR‘NR systems ( 2a − c ) has been achieved by the reaction of the mono(amino)chlorophosphine PhP(Cl)N(H)Dipp ( 1; Dipp = 2,6-( i Pr) 2 C 6 H 3 ) with 1 equiv of Li[CR‘(NR) 2 ] ( 2a, R = t Bu, R‘ = n Bu; 2b, R = Cy, R‘ = t Bu; 2c, R = Cy, R‘ = n Bu). Metalation reactions of 2a − c using n BuLi, Me 3 Al, and Bu 2 Mg have shown that the NPNCN backbone is susceptible to nucleophilic attack. Reactions of 2a or 2b with n BuLi or Me 3 Al, respectively, produce the complexes Li[DippNPhP−P( n Bu)PhNDipp]·Et 2 O ( 3 ) and Al(Me) 2 [DippNPhP−P(Me)PhNDipp] ( 4 ). These complexes involve a new type of N,N‘ bidentate ligand with a chiral phosphorus center bearing bulky organic substituents on the nitrogen atoms. Reaction of 2c with Bu 2 Mg proceeds in a different manner, producing the amidinate complex Mg[CyNC( n Bu)NCy][DippNP( n Bu)Ph]·Et 2 O ( 5 ). A more direct route to 3 and the analogous methyl-substituted complex Li[DippNPhP−P(Me)PhNDipp]·Et 2 O ( 6 ), involving the reaction of 1 with the appropriate organolithium reagent in the molar ratio 2:3, has been developed. The oxidation product of 3, {Li[DippNPhP(O)P( n Bu)PhNDipp]} 2 ( 7 ), has also been synthesized via an alternative route. Complexes 1, 2a, b, and 5 − 7 were fully characterized by multinuclear NMR spectroscopy, elemental analysis, and X-ray crystallography.
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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) | 0.001 | 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) | 0.004 | 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".