Diamidonaphthalene-Stabilized N-Heterocyclic Pnictogenium Cations and Their Cation−Cation Solid-State Interactions
Bibliographic record
Abstract
The synthesis and comprehensive characterization of a new series of N-heterocyclic phosphine, arsine, and stibine compounds is presented. The diamidochloropnictines ClPn(NR) 2 C 10 H 6 (Pn = P, As, Sb) were prepared via the dehydrohalide coupling reactions of N, N ‘-diisopropyl-1,8-diaminonaphthalene, ( i PrNH) 2 C 10 H 6, or N, N ‘-diphenyl-1,8-diaminonaphthalene, (PhNH) 2 C 10 H 6, with the appropriate pnictogen trichloride. Reaction of these pnictines with appropriate halide abstraction agents yielded the corresponding phosphenium and arsenium salts. These planar pnictogenium cations {Pn(NR) 2 C 10 H 6 } + (Pn = P, As; R = i Pr, Ph) display dicoordinate pnictogen centers that are stabilized by an electron-rich diamidonaphthalene framework and represent rare examples of six-membered N-heterocyclic pnictogenium cations possessing a π-conjugated carbon backbone. The related stibenium salts could not be prepared via this route; however, the reaction of the new heteroleptic triamidostibene, (Me 2 N)Sb( i PrN) 2 C 10 H 6, with triflic acid does generate the base-stabilized stibenium cation, [Sb( i PrN) 2 C 10 H 6 ·(Me 2 NH)] + . The phosphenium and arsenium salts exhibit different modes of packing in their solid-state structures depending upon the identity of the nitrogen substituents. The two phenyl substituted compounds display an interaction between the pnictogen center and the π-system of an adjacent naphthyl moiety. In contrast, the isopropyl substituted species undergo metastable dimerization through naphthyl π-stacking. These dimers are bound by strong dipole−dipole and dispersion interactions as revealed through computational studies.
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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 | 0.001 |
| 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) | 0.005 | 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".