Palladium(II) complexes of bis(phosphine)monooxide and bis(phosphine)monosulphide ligands bearing <i>o</i>-<i>N</i>,<i>N</i>-dimethylanilinyl substituents
Bibliographic record
Abstract
Palladium(II) complexes of bis(phosphine)monooxide and bis(phosphine)monosulphide ligands with the general formula Ar2P(CH2)nP(E)Ar2 are described (n = 1 (dmapmE), E = O, S; n = 2 (dmapeE), E = O; Ar = o-N,N-dimethylanilinyl). The precursor, PdCl2(dmapm), which exists in solution as an equilibrium mixture of the P,P- and P,N-ligated isomers, reacts with peroxides to form PdCl2(P,N-dmapmO) and with sulphur to give [PdCl(P,N,S-dmapmS)]Cl, probably by direct oxidation of the "dangling" P atom of the P,N-isomer. PdCl2(dmape), which exists in solution as a mixture of PdCl2(P,P-dmape) and [PdCl(P,P,N-dmape)]Cl, reacts with hydroxide in H2OCH2Cl2 under argon to give the face-to-face Pd(II)2 complex containing the cation [Pd2Cl2(µ-P,N:O-dmapeO)2]2+, which was isolated and crystallographically characterized as the PF6 salt. The remarkable structure, consisting of two face-to-face Pd(II) square planes in a head-to-tail orientation, reveals a 12-membered ring containing the two non-bonded metal centres (PdPd = 4.873(2) Å). The dmapmS complex shows marginal activity as a catalyst for the hydration of maleic to malic acid.Key words: phosphine, phosphine oxide, phosphine sulphide, palladium.
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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 | 0.000 |
| Insufficient payload (model declined to judge) | 0.001 | 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".