Assembly of Triangular Trimetallic Complexes by Triamidophosphine Ligands: Spin-Frustrated Mn<sup>2+</sup> Plaquettes and Diamagnetic Mg<sup>2+</sup> Analogues with a Combined Through-Space, Through-Bond Pathway for <sup>31</sup>P-<sup>31</sup>P Spin−Spin Coupling
Bibliographic record
Abstract
The reactions of 2 equiv of the ligand precursor P(CH2NHPh)3 or P[CH2NH-3,5-(CF3)2C6H3]3 with 3 equiv of Mn[N(SiMe3)2]2 provide high-yielding routes to the triangular trinuclear Mn(II) complexes [P(CH2NPh)3]2Mn3(THF)3.1.5THF and [P(CH2N-3,5-(CF3)2C6H3)3]2Mn3(THF)3. The solid-state structures of these paramagnetic complexes have approximate C3 symmetry. The magnetic moments from 300 to 1.8 K could be fit as a magnetic Jahn-Teller distorted isosceles triangle. These complexes exhibit spin frustration and possess an S = 1/2 ground state, as revealed by a plot of magnetization versus field at 1.8 K; at fields above 3.8 T, the occupation of an excited state with S = 3/2 becomes significant. The diamagnetic magnesium analogues were prepared by the reaction of the ligand precursor P(CH2NHPh)3, P[CH2NH-3,5-(CF3)2C6H3]3, or P(CH2NH-3,5-Me2C6H3)3 with nBu2Mg. The solid-state structures of [P(CH2NPh)3]2Mg3(THF)3.1.5THF and [P(CH2N-3,5-(CF3)2C6H3)3]2Mg3(THF)3 were determined. Solution 1H NMR spectroscopy was used to demonstrate that the solid-state structures are maintained in solution. The aryl group of the terminal amido donor exhibits slow rotation on the NMR time scale, and this was found to be an electronic effect. Solution 31P{1H} NMR spectroscopy revealed an unexpected 15 Hz coupling between phosphorus nuclei in these complexes. Calculations on a model complex using density functional theory demonstrates that this coupling occurs via a combined through-space, through-bond pathway.
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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 | 0.001 | 0.000 |
| Open science | 0.001 | 0.001 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.002 | 0.001 |
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".