Monometallic, homo-, and hetero-bimetallic complexes of a siloxy-bis(phosphinimide) ligand
Bibliographic record
Abstract
Deprotonation of Me3SiNP(t-Bu)2Me with BuLi generates [Me3SiNP(t-Bu)2CH2Li] (1), which reacts with (Me2SiCl)2O to give the new siloxyl-bis(phosphinimine) ligand [Me3SiNP(t-Bu)2CH2SiMe2]2O (2). This ligand reacts with 1 or 2 equiv. of CpTiCl3 to give [CpTiCl2NP(t-Bu)2CH2SiMe2OCH2SiMe2P(t-Bu)2NSiMe3] (3) and [CpTiCl2NP(t-Bu)2CH2SiMe2]2O (4), similar to the species [CpNbCl3NP(t-Bu)2CH2SiMe2]2O (5) and [CpTiCl2NP(t-Bu)2(µ-O-(CH2SiMe2)2)- P(t-Bu)2NCpNbCl3] (6). Subsequent alkylations of these metal-halide derivatives afforded the analogous permethylated analogs 7–10, respectively. Reaction of 8 with B(C6F5)3 generates [(CpTiMe2NP(t-Bu)2CH2SiMe2)(CpTiMeNP(t-Bu)2CH2SiMe2)O][MeB(C6F5)] (11). Benzylation of 4 give the species [CpTiBz2NP(t-Bu)2CH2SiMe2]2O (12), which reacts subsequently with NC(2,6-Me2C6H3) to give a 1:1 mixture of the diastereoisomers of [CpTiBz(N=C(CH2Ph)(2,6-Me2C6H3))NP(t-Bu)2CH2SiMe2]2O 13a and 13b. These synthetic routes are described and the implications considered. X-ray structural data for compounds 2, 4, 8, and 10 are reported.Key words: phosphinimide ligands, bimetallic species, heterobimetallic compounds.
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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 | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.002 | 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 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".