Bridged Dinuclear Tripodal Tris(amido)phosphane Complexes of Titanium and Zirconium as Diligating Building Blocks for Organometallic Polymers
Bibliographic record
Abstract
Abstract Appropriate bridging ligands allow for the preparation of bimetallic titanium and zirconium precursors to transition‐metal‐containing polymers using the formally trianionic P(CH 2 NAr R ) 3 ligand (where Ar R = Ph, and 3,5‐Me 2 C 6 H 3 for a and b , respectively). Lithiation of the known amidophosphane ligand precursors P(CH 2 NHAr R ) 3 ( 1a , b ) with 3 equiv. of n BuLi cleanly provided the diethyl ether adducts P(CH 2 NAr R ) 3 Li 3 (OEt 2 ) 1.5 ( 2a , b ). The THF adduct P(CH 2 NPh) 3 Li 3 (THF) 5 ( 2a‐THF ) was characterized by X‐ray crystallography. Protonolysis reactions were used to prepare the mononuclear titanium complexes P(CH 2 NAr R ) 3 TiOC 6 H 4 t Bu ( 4a , b ) and dinuclear species [P(CH 2 NPh) 3 TiNMe 2 ] 2 ‐μ‐4,4′{O[3,3′,5,5′‐(C 6 H 2 Me 2 ) 2 ]O} ( 5a ), [P(CH 2 NPh) 3 Ti] 2 (μ‐O) ( 6a ), and P(CH 2 N‐3,5‐Me 2 C 6 H 3 ) 3 Ti‐μ‐O‐Ti(NMe 2 ) 3 ( 7b ), from P(CH 2 NAr R ) 3 TiNMe 2 . The reactions of 1a , b with Zr(NEt 2 ) 4 afforded metal complexes of the type P(CH 2 NAr R ) 3 ZrNEt 2 ( 8a , b ). The chloride complexes P(CH 2 NAr R ) 3 ZrCl(THF) ( 9a , b ) were prepared by treatment of HNEt 3 Cl with 1 or 2 . The complexes 9a , b reacted with cyclopentadienyllithium (C 5 H 5 Li) to produce P(CH 2 NAr R ) 3 ZrCp ( 10a , b ), which were also prepared by the reactions of the lithium salts 2a , b with CpZrCl 3 . The dilithium salt of the fulvalene dianion (Li 2 C 10 H 8 ) reacts with 9a , b to produce the dinuclear complexes trans ‐[P(CH 2 NAr R ) 3 Zr] 2 (μ‐η 5 :η 5 ‐C 10 H 8 ) ( 10a , b ), respectively. The facile preparation of transition‐metal‐containing polymers from the bridged dinuclear complexes was illustrated by the reaction of 6a with half an equivalent of [Rh(CO) 2 (μ‐Cl)] 2 , which precipitated polymeric Cl(CO)Rh[P(CH 2 NPh) 3 Ti] 2 (μ‐O). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
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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 | 0.002 | 0.001 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 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) | 0.008 | 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 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".