Synthesis, Structure, and Reactivity of Titanium Phosphinimide Thiolate Complexes
Why this work is in the frame
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Bibliographic record
Abstract
A series of titanium−phosphinimide thiolate complexes were prepared employing either thiolate for chloride metathesis or protonolysis of metal−carbon bonds by thiols. In these ways the following species were obtained: CpTi(NPR‘ 3 )(SR) 2 (R‘ = i- Pr, R = CH 2 Ph 3; Ph 4, t- Bu 5, (SR) 2 = S 2 (CH 2 ) 2 6, S 2 (CH 2 ) 3 7, S 2 (CH 2 ) 2 C 6 H 4 8; R‘ = t- Bu, R = CH 2 Ph 9; Ph 10, t- Bu 11 ); Cp( t- Bu 3 PN)TiMe(SPh) 12; and ( t -Bu 3 PN) 2 Ti(SR) 2 (R = CH 2 Ph 14; Ph 15, t- Bu 16 ). Reactions of ( t -Bu 3 PN) 2 TiMe 2 with 1 equiv of HSCH 2 Ph gave a cyclometalated species 17, ( t -Bu 3 PN) 2 Ti( η 2 -SCHPh). The analogous reaction of 1 equiv of phenylthiol generated the species ( t -Bu 3 PN) 2 Ti(Me)(SPh) 18 . While 17 and 18 could not be isolated free of 14 and 15, respectively, the analogous reaction of tert- butylthiol afforded ( t -Bu 3 PN) 2 Ti(Me)(S t- Bu) 19 cleanly. Attempts to effect sulfur insertion into Ti−Me bonds were undertaken via the reaction of ( t -Bu 3 PN) 2 TiMe 2 with S 8 but gave instead the species ( t -Bu 3 PN) 2 Ti(η 2 -S 5 ) 20 . The reactivity of the thiolate derivatives, 3 − 5 with excess AlMe 3, was examined. Spectroscopic and crystallographic studies revealed the formation of (CpTi(μ-SR)(μ-NP i- Pr 3 )(C)(AlMe 2 ) 2 (μ-SR)AlMe (R = CH 2 Ph 21, Ph 22, t- Bu 23 ). Analogous reactions of 7 and 8 with AlMe 3 afforded [Cp( i- Pr 3 PN)Ti(SRS)]·(AlMe 3 ) 3 (R = (CH 2 ) 3 24, ((CH 2 ) 2 (C 6 H 4 )) 25 ). The mechanistic implications of the observed multiple C−H bond activation are considered. Crystallographic studies of 4, 6, 7, 14, 16, and 20 − 23 are reported.
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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 | 0.000 | 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) | 0.008 | 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 it