The impact of P-substituents on the structures, spectroscopic properties, and reactivities of POCOP-type pincer complexes of nickel(ii)
Bibliographic record
Abstract
The room temperature reaction of NiBr(2)(NCCH(3))(x) with the pincer-type ligand POCHOP(Ph) gave the new pincer complex (POCOP(Ph))NiBr (1, POCOP(Ph) = κ(P), κ(C), κ(P)-2,6-{Ph(2)PO}(2)C(6)H(3)). Complex 1 reacts with AgX to give the analogous Ni-X derivatives (X = CN, 2; OSO(2)CF(3), 3; OC(O)CH(3), 4; ONO(2), 5), whereas complex 3 reacts with phenylacetylene and NEt(3) to give the Ni-CCPh derivative 6. On the other hand, reaction of 1 or 3 with RLi or RMgI did not afford the desired Ni-R derivatives, giving instead the corresponding iodo and hydroxo derivatives. Complexes 1-6 have been characterized by NMR, IR, and UV-Vis spectroscopy and X-ray crystallography. The solid state structural and IR data indicate that Ni-C(sp) interaction is dominated by ligand-to-metal σ-donation in 2 and 6. Cyclic voltammetry measurements indicate that complexes 3 and 4 display reversible redox behaviour (Ni(II)/Ni(III)); comparison of the E(0)(1/2) values for these complexes and their POCOP(i-Pr) analogues shows that both the X ligands and the P-substituent have a considerable impact on the ease of oxidation in this family of complexes.
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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 | 0.001 |
| Meta-epidemiology (narrow) | 0.001 | 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 | 0.000 |
| 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".