Thallium(i) complexes of dichalcogenido imidodiphosphinates {Tl[(EPiPr2)2N]}n (E = Te, Se, S): Synthesis, NMR spectra and a structural comparison
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Bibliographic record
Abstract
The homoleptic thallium(i) complexes {Tl[(EP(i)Pr(2))(2)N]}(n) (, E = Te; , E = Se; , E = S) have been obtained in 70-86% yields from the reaction of TlOEt with (TMEDA)Na[(EP(i)Pr(2))(2)N] in CH(2)Cl(2) or Et(2)O. Complexes were structurally characterised in the solid state by single crystal X-ray diffraction and in solution by multinuclear NMR spectroscopy ((31)P, (77)Se, and (125)Te). The solid-state structures of , and are comprised of one-dimensional coordination polymers. In and there are two distinct environments for both the thallium centres and the [(EP(i)Pr(2))(2)N](-) ligands. The denticities of the selenium centres in the ligands of differ significantly from those of tellurium donor atoms in giving rise to different coordination geometries at the chalcogen atoms in these two complexes; however, both possess edge-sharing Tl(2)E(4) octahedra as structural units. By contrast, the sulfur analogue exhibits only one ligand environment with trigonal pyramidal geometries for both sulfur centres and a distorted tetrahedral geometry for thallium generating vertex-sharing four-membered Tl(2)S(2) rings.
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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) | 0.001 | 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) | 0.003 | 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