Synthesis and Characterization of the M(II) (M = Ge, Sn, or Pb) Phosphinidene Dimers {M(μ-PAr′)}<sub>2</sub> (Ar′ = C<sub>6</sub>H<sub>3</sub>-2,6-(C<sub>6</sub>H<sub>3</sub>-2,6-Pr<sup><i>i</i></sup><sub>2</sub>)<sub>2</sub>)
Bibliographic record
Abstract
Reaction of M{N(SiMe(3))(2)}(2) (M = Ge, Sn, or Pb) with the sterically encumbered primary phosphine Ar'PH(2) (2), Ar' = C(6)H(3)-2,6-(C(6)H(3)-2,6-Pr(i)(2)), at ca. 200 °C afforded the highly colored phosphinidene dimers {M(μ-PAr')}(2), M = Ge(3), Sn(4), or Pb(5), with disilylamine elimination. The compounds were characterized by single-crystal X-ray crystallography and heteronuclear NMR spectroscopy. The structures of 3, 4, and 5 featured similar M(2)P(2) ring cores, of which 4 and 5 have 50/50 P atom disorder, consistent with either a planar four-membered M(2)P(2) arrangement with anti aryl groups or with an M(2)P(2) ring folded along the M-M axis with syn aryl groups. A syn-folded structure was resolved for the Ge(2)P(2) ring in compound 3. The M-P distances resembled those in M(II) phosphido complexes and are consistent with single bonding. The coordination geometries at the phosphorus atoms are pyramidal. DFT calculations on the gas phase models {M(μ-PMe)}(2) (M = Ge, Sn, Pb) agreed with the syn (M-M folded) structural interpretation of the X-ray data. The synthesis of the bulky phosphine Ar'PH(2) 2 with the use of the aryl transfer agent Ar'MgBr(THF)(2) is also reported. This route afforded a significantly higher yield of product than that which was obtained using LiAr', which tends to result in aryl halide elimination and the observation of insoluble red phosphorus.
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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 | 0.000 | 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".