Aminoalkyl-Substituted Indenylnickel(II) Complexes (<i>η</i><sup>3</sup>:<i>η</i><sup>0</sup>-Ind(CH<sub>2</sub>)<sub>2</sub>NMe<sub>2</sub>)Ni(PR<sub>3</sub>)X and [(<i>η</i><sup>3</sup>:<i>η</i><sup>1</sup>-Ind(CH<sub>2</sub>)<sub>2</sub>NMe<sub>2</sub>)Ni(PR<sub>3</sub>)][BPh<sub>4</sub>]: Influence of the Phosphine in Ligand Exchange and Polymerization Reactions
Bibliographic record
Abstract
Reaction of LiInd(CH 2 ) 2 NMe 2 with (PR 3 ) 2 NiCl 2 gave the neutral complexes ( η 3: η 0 -Ind(CH 2 ) 2 NMe 2 )Ni(PR 3 )Cl (R = Ph ( 1 ) or Me ( 2 )), while the PCy 3 analogue, ( η 3: η 0 -Ind(CH 2 ) 2 NMe 2 )Ni(PCy 3 )Cl ( 3 ), was obtained by reacting 1 with PCy 3 . These Ni−Cl species react with R‘Li or NaBPh 4 to form, respectively, the corresponding Ni−R‘ derivatives ( η 3: η 0 -Ind(CH 2 ) 2 NMe 2 )Ni(PR 3 )R‘ (R = Ph, R‘ = Me ( 4 ) or CCPh ( 5 ); R = R‘ = Me ( 6 )) or the cationic species [( η 3: η 1 -Ind(CH 2 ) 2 NMe 2 )Ni(PR 3 )] + (R = Ph ( 7 ), Me ( 8 ), or Cy ( 9 )), in which the NMe 2 moiety is coordinated to the nickel center. These complexes have been fully characterized, including solid state structure determinations by X-ray crystallography for complexes 2, 4, 5, 6, and 9 . Inspection of the structural data showed that replacing the Cl ligand by the more strongly donating ligands CCPh and Me reinforces the Ni−P and Ni−Ind interactions. On the other hand, electrochemical measurements showed that the reduction potentials of the Ni−Cl compounds are intermediate between the Ni−R‘ derivatives, which are more resistant to reduction, and the cationic species, which are the easiest to reduce. The cationic complexes are single-component catalysts for the polymerization of styrene, giving poly(styrene) with M w in the range of 10 4 −10 5, and the hydrosilylation of styrene and 1-hexene with PhSiH 3 and Ph 2 SiH 2 . The nature of the phosphine ligand has an important influence on the catalytic reactivities, the PMe 3 analogue 8 being the most active catalyst.
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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 | 0.009 | 0.007 |
| Meta-epidemiology (narrow) | 0.016 | 0.017 |
| Meta-epidemiology (broad) | 0.016 | 0.007 |
| Bibliometrics | 0.008 | 0.024 |
| Science and technology studies | 0.009 | 0.010 |
| Scholarly communication | 0.005 | 0.010 |
| Open science | 0.011 | 0.008 |
| Research integrity | 0.010 | 0.014 |
| Insufficient payload (model declined to judge) | 0.001 | 0.002 |
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; both teacher heads agree on what is shown here.
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".