Functionalizing Titanium−Phosphinimide Complexes
Bibliographic record
Abstract
The reaction of the titanacycle CpTi(NP t- Bu 3 )(C 4 H 8 ) ( 1 ) with benzyl halides, 4-bromo-1-butene, and allyl chloride proceeds with loss of ethylene to give CpTiX(NP t- Bu 3 )(CH 2 Ph) (X = Cl, 3; Br, 4 ), CpTiBr(NP t- Bu 3 )(CH 2 CH 2 CHCH 2 ) ( 5 ), and CpTiCl(NP t- Bu 3 )(CH 2 CHCH 2 ) ( 6 ), respectively. Complexes 4 and 6 were readily alkylated to CpTiMe(NP t- Bu 3 )(CH 2 Ph) ( 7 ) and CpTiMe(NP t- Bu 3 )(CH 2 CHCH 2 ) ( 8 ), respectively. Loss of ethylene also occurs on reaction of 1 with bipyridine to give CpTi(NP t- Bu 3 )(bipy) ( 9 ). In contrast, reaction of 1 with ClSiMePh 2 in the presence of PMe 3 gave CpTiCl(NP t- Bu 3 )(CH 2 CH 2 SiPh 2 Me) ( 10 ). In a similar fashion, the two-carbon derivatives CpTiCl(NP t- Bu 3 )(CH 2 CH 2 SiMe 3 ) ( 11 ), CpTiCl(NP t- Bu 3 )(CH 2 CH 2 Si(SiMe 3 ) 3 ) ( 12 ), CpTi(NP t- Bu 3 )(CH 2 CH 2 SiMe 3 )(OSO 2 CF 3 ) ( 13 ), CpTiCl(NP t- Bu 3 )(CH 2 CH 2 Sn n -Bu 3 ) ( 14 ), CpTiCl(NP t- Bu 3 )(CH 2 CH 2 SiCl 3 ) ( 15 ), and [CpTiCl(NP t- Bu 3 )(CH 2 CH 2 )] 2 SiCl 2 ( 16 ) were produced. In the absence of PMe 3, reaction of 1 with SiCl 4 and ClSnMe 3 gave the four-carbon derivatives CpTiCl(NP t- Bu 3 )(CH 2 CH 2 CH 2 CH 2 SiCl 3 ) ( 17 ) and CpTiCl(NP t- Bu 3 )(CH 2 CH 2 CH 2 CH 2 SnMe 3 ) ( 18 ), while reaction of 1 with ClSnPh 3 gave only the two-carbon chain derivative CpTiCl(NP t- Bu 3 )(CH 2 CH 2 SnPh 3 ) ( 19 ). Nonetheless, in the presence and absence of PMe 3 reaction of 1 with ClBcat or ClPPh 2 gave the analogous two- and four-carbon derivatives CpTiCl(NP t- Bu 3 )(CH 2 CH 2 Bcat) ( 20 ), CpTiCl(NP t- Bu 3 )(CH 2 CH 2 CH 2 CH 2 Bcat) ( 21 ), CpTiCl(NP t- Bu 3 )(CH 2 CH 2 PPh 2 )( 22 ), and CpTiCl(NP t- Bu 3 )(CH 2 CH 2 CH 2 CH 2 PPh 2 ) ( 23 ), respectively. The corresponding species CpTiCl(NP t- Bu 3 )(CH 2 CH(CH 3 )CH(CH 3 )CH 2 PPh 2 ) ( 24 ) was prepared from CpTi(NP t- Bu 3 )(CH 2 CHMe) 2 ( 2 ), while complexation of 23 and 24 afforded CpTiCl(NP t- Bu 3 )(CH 2 CH 2 CH 2 CH 2 PPh 2 )RhCl(cod) ( 25 ) and CpTiCl(NP t- Bu 3 )(CH 2 CH(CH 3 )CH(CH 3 )CH 2 PPh 2 )RhCl(cod) ( 26 ). The mechanisms affording the functionalized two- and four-carbon derivatives above are discussed and the implications considered.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
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) | 0.001 | 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 | 0.001 |
| Research integrity | 0.001 | 0.001 |
| 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 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".