Lanthanide Complexes of Boraamidinate Ligands: Synthesis and X-ray Structures of {[Li(THF)<sub>4</sub>][<i>bam</i>LnCl<sub>2</sub>(THF)]}<sub>2</sub> (<i>bam</i> = [PhB(NDipp)<sub>2</sub>]<sup>2−</sup>; Ln = Y, Pr, Nd, Sm, Ho, Er, Yb) and {<i>bam</i>LnCl(THF)<sub>2</sub>}<sub>2</sub> (Ln = Y, Sm)
Bibliographic record
Abstract
The first examples of the incorporation of the boraamidinate ligand into lanthanide complexes have been prepared by reaction of equimolar amounts of [Li(2)][PhB(NDipp)(2)] and LnCl(3) in tetrahydrofuran (THF), which produces "ate" complexes of the form {[Li(THF)(4)][bamLnCl(2)(THF)]}(2) [Ln = Y (9a), Pr (9b), Nd (9c), Sm (9d), Ho (9e), Er (9f), Yb (9g)] through the inclusion of the LiCl by-product. The isostructural complexes 9a-g were characterized in the solid state by X-ray crystallography, which revealed ion-separated complexes composed of a dimeric anion with a terminal and a bridging chloride ligand on each metal center and a tetrasolvated cation, [Li(THF)(4)](+). In solution, the yttrium complex 9a was characterized by multinuclear ((1)H, (13)C, (7)Li, and (11)B) NMR spectroscopy. The (1)H and (7)Li NMR spectra of the paramagnetic complexes 9b-9d showed broad resonances, but NMR spectra could not be obtained for 9e-g. The complexes 9a-g are readily soluble in THF, but insoluble in diethyl ether and hexane. The reaction of {[Li(THF)(4)][bamLnCl(2)(THF)]}(2) (Ln = Y, Sm) with an excess of trimethysilyl trifluoromethanesulfonate (TMSOTf) generates the dimeric neutral complexes {bamLnCl(THF)(2)}(2), which have been characterized by (1)H NMR and X-ray crystallography.
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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 | 0.003 | 0.003 |
| Meta-epidemiology (narrow) | 0.007 | 0.008 |
| Meta-epidemiology (broad) | 0.009 | 0.003 |
| Bibliometrics | 0.002 | 0.005 |
| Science and technology studies | 0.002 | 0.005 |
| Scholarly communication | 0.002 | 0.002 |
| Open science | 0.006 | 0.005 |
| Research integrity | 0.005 | 0.006 |
| 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; both teacher heads agree on what is shown here.
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".