Syntheses and X-ray Structures of Potassium Derivatives and a Paramagnetic Nickel(II) Complex of a Cyclodiphosph(III/V)azane Monoselenide
Bibliographic record
Abstract
The cyclodiphosph(III/V)azane monoselenide [(t)Bu(H)N(Se)P(micro-N(t)Bu)(2)PN(H)(t)Bu] (6, H(2)cdppSe where cdpp = cyclodiphosphazane) is obtained in quantitative yield from the comproportionation reaction of equimolar amounts of H(2)cdpp (7) and H(2)cdppSe(2) (3) in toluene at 85 degrees C. The X-ray structures of 3 and 6 reveal that both the monoselenide and the diselenide adopt a cis,endo,exo arrangement of the (t)BuNH groups. Metalation of 6 with 1 equiv of KO(t)Bu or 2 equiv of KCH(2)Ph in THF produces [(THF)K[HcdppSe]](2) (8) or [[(THF)(2)K](2)[cdppSe]](2) (9), respectively. The initial deprotonation involves the (t)BuNH group attached to the P(V) center in 6. In the dimeric structure of 8, both of the monoanionic ligands are bis-N,Se-chelated to the two K(+) cations to give a distorted K(2)N(2)Se(2) octahedron. In the centrosymmetric dimer 9, the dianionic ligands adopt two different coordination modes to the bis-solvated K(+) ions, viz., tridentate N,N',N" coordination and N,Se-chelation involving both exo- and endocyclic nitrogen atoms. The dimer is linked through K-Se interactions. The reaction of 2 equiv of 8 with NiCl(2)(PMe(3))(2) in THF produces [Ni(HcdppSe)(2)], which has a distorted tetrahedral structure and exhibits anomalous (1)H, (13)C, and (31)P NMR chemical shifts owing to the proximity of the paramagnetic Ni(II) center.
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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 | 0.000 | 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".