Synthesis, Structure, and Reactivity of Titanium Phosphinimide Thiolate Complexes
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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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) | 0.000 | 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 | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.001 | 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 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".