Preparation and X-ray Structures of Alkali-Metal Derivatives of the Ambidentate Anions [<sup>t</sup>BuN(E)P(<i>μ</i>-N<sup>t</sup>Bu)<sub>2</sub>P(E)N<sup>t</sup>Bu]<sup>2</sup><sup>-</sup> (E = S, Se) and [<sup>t</sup>BuN(Se)P(μ-N<sup>t</sup>Bu)<sub>2</sub>PN(H)<sup>t</sup>Bu)]<sup>-</sup>
Bibliographic record
Abstract
The ambidentate dianions [(t)BuN(E)P(mu-N(t)Bu)(2)P(E)N(t)Bu](2)(-) (5a, E = S; 5b, E = Se) are obtained as their disodium and dipotassium salts by the reaction of cis-[(t)Bu(H)N(E)P(mu-N(t)Bu)(2)P(E)N(H)(t)Bu] (6a, E = S; 6b, E = Se), with 2 equiv of MN(SiMe(3))(2) (M = Na, K) in THF at 23 degrees C. The corresponding dilithium derivative is prepared by reacting 6a with 2 equiv of (t)BuLi in THF at reflux. The X-ray structures of five complexes of the type [(THF)(x)()M](2)[(t)BuN(E)P(mu-N(t)Bu)(2)P(E)N(t)Bu] (9, M = Li, E = S, x = 2; 11a/11b, M = Na, E = S/Se, x = 2; 12a, M = K, E = S, x = 1; 12b, M = K, E = Se, x = 1.5) have been determined. In the dilithiated derivative 9 the dianion 5a adopts a bis (N,S)-chelated bonding mode involving four-membered LiNPS rings whereas 11a,b and 12a,b display a preference for the formation of six-membered MNPNPN and MEPNPE rings, i.e., (N,N' and E,E')-chelation. The bis-solvated disodium complexes 11a,b and the dilithium complex 9 are monomeric, but the dipotassium complexes 12a,b form dimers with a central K(2)E(2) ring and associate further through weak K.E contacts to give an infinite polymeric network of 20-membered K(6)E(6)P(4)N(4) rings. The monoanions [(t)Bu(H)N(E)P(mu-N(t)Bu)(2)P(E)N(t)Bu)](-) (E = S, Se) were obtained as their lithium derivatives 8a and 8b by the reaction of 1 equiv of (n)BuLi with 6a and 6b, respectively. An X-ray structure of the TMEDA-solvated complex 8a and the (31)P NMR spectrum of 8b indicate a N,E coordination mode. The reaction of 6b with excess (t)BuLi in THF at reflux results in partial deselenation to give the monolithiated P(III)/P(V) complex [(THF)(2)Li[(t)BuN(Se)P(mu-N(t)Bu)(2)PN(H)(t)Bu]] 10, which adopts a (N,Se) bonding mode.
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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) | 0.002 | 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".