Nickel(0) catalyzed carbon-hydrogen bond activation: A mechanistic study of the formation of a nickel(I)-nickel(I) complex.
Bibliographic record
Abstract
The first part of this thesis deals with a mechanistic investigation into the conversion of the known benzyne complex, Ni(eta2-C 6H2F2)(PEt3)2, to the novel dinuclear Ni(I)-Ni(I) complex, (PEt3)4Ni2(eta 2-C6H2-4,5-F2)2. The coupling of two molecules of Ni(eta2-C6H2F 2)(PEt3)2 does not result in the formation of (PEt3)4Ni2(eta2-C6 H2-4,5-F2)2. There is a rearrangement in the disposition of the hydrogen atoms from para disposed in Ni(eta 2-C6H2F2)(PEt3)2 to ortho disposed in (PEt3)4Ni2(eta 2-C6H2-4,5-F2)2, which was found to be the result of C-H bond activation catalyzed by Ni(0). Proposed mechanisms involving the isolated reaction intermediates Ni2(mu-eta 2:eta2-C6H2F2)(PEt 3)2 and (PEt3)2(PMe3) 2Ni2(eta2-C6H2-3,4-F 2)2 are given and supported by 19F NMR spectroscopy and deuterium labelling studies. The second part of this thesis deals with the formation and characterization of an organized transition metal cluster. A novel tripodal ligand design was developed that involves both amido and phosphine donor groups. An organized copper(I) cluster, [P(CH2NC6H3-3,5-(CF 3)3)3]2Cu9(mu-2,4,6-Me 3C6H2)3 was synthesized by reacting the ligand, [P(CH2NC6H3-3,5-(CF3) 3)3], with mesitylcopper. The cluster contains eight copper(I) centres arranged in a zig-zag motif around a central copper(I) atom and is soluble in pentane. Source: Masters Abstracts International, Volume: 45-01, page: 0323. Thesis (M.Sc.)--University of Windsor (Canada), 2006.
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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 | 0.001 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.002 | 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 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".