Dialkylscandium Complexes Supported by β-Diketiminato Ligands: Synthesis, Characterization, and Thermal Stability of a New Family of Organoscandium Complexes
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Bibliographic record
Abstract
Several diorganoscandium complexes stabilized by the β-diketiminato ligands (Ar)NC(R)CHC(R)N(Ar) (Ar = 2,6- i Pr-C 6 H 3; R = CH 3 (ligand a ), R = t Bu (ligand b )) have been synthesized. Reaction of the lithium salts of the ligands with ScCl 3 ·3THF leads to the complexes LScCl 2 (THF) n, which may be readily alkylated to form the dialkyl derivatives. Most are isolated as base-free, four-coordinate complexes. Several have been characterized via X-ray crystallography, and a detailed discussion of their structures is presented. Steric interactions between Ar and the Sc−alkyl groups force the scandium to adopt an out-of-plane bonding mode. In solution, this is manifested via a fluxional process which equilibrates the two diastereotopic alkyl groups and ligand groups as well. The barriers to this process roughly correlate with the steric bulk of the alkyl substituents. At elevated temperatures, the dialkyl derivatives LScR 2 undergo a metalation process whereby one of the alkyl groups is eliminated as RH, and a ligand i Pr group is metalated in the methyl position. These reactions are first order in scandium complex, and activation parameters of Δ H ⧧ = 19.7(6) kcal mol - 1 and Δ S ⧧ = −17(2) cal mol - 1 K - 1 were measured for the loss of Me 4 Si from (Lig b )Sc(CH 2 SiMe 3 ) 2 .
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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) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.035 | 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