Four‐Membered Heterometallacyclic d <sup>0</sup> and d <sup>1</sup> Complexes of Group 4 Metallocenes with Amidato Ligands
Bibliographic record
Abstract
A study of the coordination chemistry of different amidato ligands [(R)N-C(Ph)O] (R=Ph, 2,6-diisopropylphenyl (Dipp)) at Group 4 metallocenes is presented. The heterometallacyclic complexes [Cp2M(Cl){κ(2)-N,O-(R)N-C(Ph)O}] M=Zr, R=Dipp (1 a), Ph (1 b); M=Hf, R=Ph (2)) were synthesized by reaction of [Cp2MCl2] with the corresponding deprotonated amides. Complex 1 a was also prepared by direct deprotonation of the amide with Schwartz reagent [Cp2Zr(H)Cl]. Salt metathesis reaction of [Cp2Zr(H)Cl] with deprotonated amide [(Dipp)N-C(Ph)O] gave the zirconocene hydrido complex [Cp2M(H){κ(2)-N,O-(Dipp)N-C(Ph)O}] (3). Reaction of 1 a with Mg did not result in the desired Zr(III) complex but in formation of Mg complex [(py)3Mg(Cl) {κ(2)-N,O-(Dipp)N-C(Ph)O}] (4; py=pyridine). The paramagnetic complexes [Cp'2Ti{κ(2)-N,O-(R)N-C(Ph)O}] (Cp'=Cp, R=Ph (7 a); Cp'=Cp, R=Dipp (7 b); Cp'=Cp*, R=Ph (8)) were prepared by the reaction of the known titanocene alkyne complexes [Cp2'Ti(η(2)-Me3SiC2SiMe3)] (Cp'=Cp (5), Cp'=Cp* (6)) with the corresponding amides. Complexes 1 a, 2, 3, 4, 7 a, 7 b, and 8 were characterized by X-ray crystallography. The structure and bonding of complexes 7 a and 8 were also characterized by EPR spectroscopy.
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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 | 0.001 | 0.000 |
| Meta-epidemiology (narrow) | 0.001 | 0.001 |
| 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 | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.010 | 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 teacher head, 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".