Cationic Methyl- and Chlorotitanium Phosphinimide Complexes
Bibliographic record
Abstract
A variety of donor-stabilized cationic complexes of the form [Cp(NP t- Bu 3 )TiMe(L)][MeB(C 6 F 5 ) 3 ] and [Cp(NP t- Bu 3 )TiMe(L)][B(C 6 F 5 ) 4 ] (L = Py, 4-EtPy, 4- t -BuPy, NC 5 H 4 NMe 2, PMe 3, P n -Bu 3, PPh 3, P( p -MeC 6 H 4 ) 3 )have been prepared and characterized. Prolonged storage in CH 2 Cl 2 solution resulted in chloride for methyl exchange to afford species of the form [CpTi(NP t- Bu 3 )Cl(L)][B(C 6 F 5 ) 4 ], [{CpTi(NP t -Bu 3 )Me} 2 (μ-Cl)][B(C 6 F 5 ) 4 ], and [CpTi(NP t -Bu 3 )(μ-Cl)] 2 [MeB(C 6 F 5 ) 3 ] 2 . The byproduct salt [( o- MeC 6 H 4 ) 3 PCH 2 Cl][B(C 6 F 5 ) 4 ] was obtained from reactions employing the sterically demanding donor phosphine P( o- MeC 6 H 4 ) 3, suggesting transient generation of the cation [CpTi(NP t- Bu 3 )Cl(CH 2 Cl 2 )] + . Analogous reactivity was not seen in C 6 H 5 Cl, although the species [{CpTi(NP t -Bu 3 )Me} 2 (μ-Me)][B(C 6 F 5 ) 4 ] could be formed in this solvent. The isolated zwitterionic complex TiCp(NP t -Bu 3 )Me(μ-MeB(C 6 F 5 ) 3 ) readily performs insertion chemistry into the Ti−methyl bonds with diisopropylcarbodiimide and diphenylacetylene substrates to afford the cationic species [CpTi(NP t -Bu 3 )((N i -Pr) 2 CMe)][MeB(C 6 F 5 ) 3 ], [TiCp(NP t -Bu 3 )(PhCCPh(Me))][MeB(C 6 F 5 ) 3 ], and [TiCp(NP t -Bu 3 )(PhCCPh(Me))(PMe 3 )][MeB(C 6 F 5 ) 3 ]. The implications of this chemistry are considered.
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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 | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| 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".