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 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) | 0.000 | 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) | 0.067 | 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".