Structure and Reactivity of the Cationic Nickel Compound [(η<sup>3</sup>:η<sup>1</sup>-Ind(CH<sub>2</sub>)<sub>2</sub>NMe<sub>2</sub>)Ni(PPh<sub>3</sub>)][BPh<sub>4</sub>]
Bibliographic record
Abstract
The solid-state structure of the first nickel compound containing a chelating amino−indenyl ligand, [(η 3:η 1 -Ind(CH 2 ) 2 NMe 2 )Ni(PPh 3 )][BPh 4 ] ( 2 ), has been resolved and confirms the chelation of the amine tether to the nickel center. Complex 2 acts as a precatalyst for the oligomerization of norbornene, the dimerization of phenylsilane, and the polymerization of styrene. The results of these catalytic reactions are qualitatively different from those catalyzed by the cationic species generated in situ from the precursor complex (η 3:η 0 -Ind(CH 2 ) 2 NMe 2 )Ni(PPh 3 )Cl ( 1 ). Phosphines displace the amine tether in 2 to give the bis(phosphine) cations [(η 3:η 0 -Ind(CH 2 ) 2 NMe 2 )Ni(Ph 2 PCH 2 CH 2 PPh 2 )] + ( 3 ) and [(η 3:η 0 -Ind(CH 2 ) 2 NMe 2 )Ni(PPh 3 )(PR 3 )] + ( 4, R = Ph; 5, R = Me), whereas LiI reacts to form the neutral compound [(η 3:η 0 -Ind(CH 2 ) 2 NMe 2 )Ni(PPh 3 )I]·LiBPh 4 ( 7 ). The displacement of the amine tether by pyridine and its methyl-substituted derivatives leads to an equilibrium between 2 and [(η 3:η 0 -Ind(CH 2 ) 2 NMe 2 )Ni(PPh 3 )L] + ( 6 ) with K eq values of 9 ( 6a, L = pyridine), 2.0 ( 6b, L = 2-picoline), 23 ( 6c, L= 3-picoline), 33 ( 6d, L = 4-picoline), and 16 ( 6e, L = 3,5-lutidine).
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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 | 0.002 |
| Meta-epidemiology (narrow) | 0.004 | 0.004 |
| Meta-epidemiology (broad) | 0.005 | 0.003 |
| Bibliometrics | 0.001 | 0.006 |
| Science and technology studies | 0.003 | 0.003 |
| Scholarly communication | 0.001 | 0.002 |
| Open science | 0.004 | 0.003 |
| Research integrity | 0.003 | 0.004 |
| 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; 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".