Synthesis and exchange reactions of Ni-dimine-COD, acetylene and olefin complexes
Bibliographic record
Abstract
The complexes MesDADNi(COD) (1), DippDADNi(COD) (2), DippDABNiCOD (3) and DippBIANNi(COD) (5) were readily prepared from Ni(COD)(2). The analogous reaction of the ligand MesBIAN afforded (MesBIAN)(2)Ni (4). The related Ni alkyne complexes DADNi(PhC[triple bond]CPh) (6), DippDABNi(PhC[triple bond]CPh) (7) and DippBIANNi(PhC[triple bond]CPh) (8) are readily prepared by addition of alkyne to solutions of the COD species. The analogous reactions employing tBuDAD ligand with either Ni(COD)(2) alone or Ni(COD)(2) and PhC[triple bond]CPh led only to the known bis-ligand Ni complex, although tBuDADNi(MeCO(2)C[triple bond]CCO(2)Me) (9) is readily prepared. In a similar fashion, the species DippDADNi(MeCO(2)C[triple bond]CCO(2)Me) (10), DippDABNi(Me(3)SiC[triple bond]CSiMe(3)) (11), DippDABNi(MeCO(2)C[triple bond]CCO(2)Me) (12) and DippBIANNi(MeCO(2)C[triple bond]CCO(2)Me) (13) were prepared. Reactions with olefins afforded DippDABNi(MeCO(2)CH=CHCO(2)Me) (14), DippDABNi(MeCO(2)CH=CHPh) (15). Employing isolated (3) or (15) in exchange reactions afforded (7), (11) (14) and (15). Similarly (6) served as a precursor to (10) while (11) reacts with PhC[triple bond]CPh to give (7). The solid state structures of (1), (3)-(7), (9), (11) and (15) 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 | 0.001 |
| 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".