Phosphinimido Complexes of Silicon, Tin, and Germanium
Bibliographic record
Abstract
The preparation of a silyl−phosphinimide of the form (R 3 PN)SiMe 3 (R = Me ( 1 ), i- Pr ( 2 ), Ph ( 3 ), t- Bu ( 4 )) was achieved by the conventional literature methodology of oxidation of phosphine by N 3 SiMe 3 . The analogous species ( t- Bu 3 PN)MMe 3 (M = Ge ( 5 ), Sn ( 6 )) were derived via a stoichiometric reaction of the salt Li[NP -t- Bu 3 ] with Me 3 MCl. Similarly, the species ( t- Bu 3 PN) 2 MMe 2 (M = Si ( 7 ), Ge ( 8 ), Sn ( 9 )), ( i- Pr 3 PN)SnMe 3 ( 10 ), ( i- Pr 3 PN) 2 SnMe 2 ( 11 ), and ( t -Bu 3 PN) 2 SnMeCl ( 12 ) were prepared. Subsequent reactions of 12 afforded ( t -Bu 3 PN) 3 SnMe ( 13 ) and ( t -Bu 3 PN) 2 Sn(O t -Bu)Me ( 14 ). In analogous metathesis reactions R 3 PNSnPh 3 (R = t- Bu ( 15 ), i- Pr ( 16 )), ( t -Bu 3 PN) 2 SnPh 2 ( 17 ), and ( t -Bu 3 PN) 2 Sn( t -Bu) 2 ( 18 ) were also prepared. Reaction of i -Pr 3 PNH and ClSnMe 3 gave ( i- Pr 3 PNH)SnMe 3 Cl ( 19 ), whereas 6 was obtained from the reaction of t- Bu 3 PNH with Me 3 SnCl. The reaction of 1 with B(C 6 F 5 ) 3 resulted in the formation of Me 3 PN(SiMe 3 )B(C 6 F 5 ) 3 ( 20 ), whereas the phosphinimines 2 and 3 react with B(C 6 F 5 ) 3 in a 2:1 ratio to give [R 3 PNSiMe 2 (N(PR 3 )SiMe 3 )][MeB(C 6 F 5 ) 3 ] (R = i- Pr ( 21 ), Ph ( 22 )). In contrast, reaction of 4 and 6 with B(C 6 F 5 ) 3 afforded [((μ- t- Bu 3 PN)MMe 2 ) 2 ][MeB(C 6 F 5 ) 3 ] 2 (M = Si ( 23 ), Sn ( 24 )). The analogous reaction of 7 and 9 with B(C 6 F 5 ) 3 gave products formulated as [(( t -Bu 3 PN) 2 MMe) 2 ][MeB(C 6 F 5 ) 3 ] 2 (M = Si ( 25 ), Sn ( 26 )) and [(( i -Pr 3 PN) 2 SnMe) 2 ][MeB(C 6 F 5 ) 3 ] 2 ( 27 ). Complexes 7 − 9, 17, 19, 20, and 24 were characterized crystallographically. The implications of this chemistry with regard to the steric demands of phosphinimide ligands 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) | 0.018 | 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".