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 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 | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.002 | 0.001 |
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".