Synthesis, Structure, and Reactivity of the Phosphinimide Complexes (<i>t-</i>Bu<sub>3</sub>PN)<i><sub>n</sub></i>MX<sub>4</sub><sub>-</sub><i><sub>n</sub></i> (M = Ti, Zr)
Why this work is in the frame
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Bibliographic record
Abstract
The phosphinimide complexes ( t- Bu 3 PN)TiCl 3 ( 1 ) and ( t- Bu 3 PN) 2 TiCl 2 ( 4 ) are readily prepared in high yields from the stoichiometric reaction of t- Bu 3 PNSiMe 3 and TiCl 4, while ( t- Bu 3 PN) 3 TiCl ( 11 ) is readily obtained from the reaction of t- Bu 3 PNLi and TiCl 4 . The analogous 1:1 or 2:1 reactions of ZrCl 4 and t- Bu 3 PNLi afford mixtures of products, although in the 3:1 stoichiometric ratio ( t -Bu 3 PN) 3 ZrCl ( 12 ) is isolable. These complexes are readily alkylated with a variety of reagents to give ( t- Bu 3 PN)TiMe 3 ( 2 ), ( t- Bu 3 PN)Ti(CH 2 Ph) 3 ( 3 ), ( t -Bu 3 PN) 2 TiMe 2 ( 5 ), ( t- Bu 3 PN) 2 Ti(η 3 -C 3 H 5 ) 2 ( 6 ), ( t- Bu 3 PN) 2 Ti(CH 2 Ph) 2 ( 7 ), ( t- Bu 3 PN) 2 TiPh 2 ( 8 ), ( t- Bu 3 PN) 2 Ti(η 5 -Cp)Cl ( 9 ), ( t- Bu 3 PN) 2 Ti(η 5 -Cp)Me ( 10 ), ( t- Bu 3 PN) 3 TiMe ( 13 ), ( t- Bu 3 PN) 3 TiPh ( 14 ), ( t -Bu 3 PN) 3 ZrMe ( 15 ), ( t -Bu 3 PN) 3 Zr(CH 2 Ph) ( 16 ), and ( t -Bu 3 PN) 3 Zr(η 5 -Cp) ( 17 ). Subsequent reactions of some of these alkyl derivatives with [PhNMe 2 H][B(C 6 F 5 ) 4 ], [Ph 3 C][B(C 6 F 5 ) 4 ], or B(C 6 F 5 ) 3 are investigated. A number of zwitterionic and cationic species complexes have been characterized. These include [(t-Bu 3 PN)Ti(CH 2 Ph) 2 (PhCH 2 )B(C 6 F 5 ) 3 ] ( 18 ), [( t- Bu 3 PN) 2 TiMe(PMe 3 )][B(C 6 F 5 ) 4 ] ( 19 ), ( t- Bu 3 PN) 2 TiMe (μ-MeB(C 6 F 5 ) 3 ) ( 20 ), ( t- Bu 3 PN) 2 Ti(μ-MeB(C 6 F 5 ) 3 ) 2 ( 21 ), and ( t- Bu 3 PN) 2 Ti(C 6 F 5 ) 2 ( 22 ). The implications of this chemistry are considered. Structural data for 1, 4, 5, 12, 16, 21, and 22 are described.
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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 | 0.002 | 0.001 |
| Meta-epidemiology (narrow) | 0.004 | 0.004 |
| Meta-epidemiology (broad) | 0.005 | 0.003 |
| Bibliometrics | 0.001 | 0.005 |
| Science and technology studies | 0.002 | 0.003 |
| Scholarly communication | 0.001 | 0.002 |
| Open science | 0.004 | 0.002 |
| Research integrity | 0.002 | 0.003 |
| Insufficient payload (model declined to judge) | 0.003 | 0.001 |
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