Manganese(II) Alkyl/π-Allyl Complexes Resistant to Ligand Redistribution
Bibliographic record
Abstract
The reaction of [Li(THF) 4 ][(Mn{C(SiMe 3 ) 3 }) 3 (μ-Cl) 4 (THF)] ( 1 ) with K(allyl TMS2 ) (allyl TMS2 = 1,3-C 3 H 3 (SiMe 3 ) 2 ) afforded [(η 3 -allyl TMS2 )Mn{C(SiMe 3 ) 3 }{ClLi(THF) 3 }] ( 2 ). Attempted sublimation of 2 yielded [(η 3 -allyl TMS2 )Mn{C(SiMe 3 ) 3 }(THF)] ( 3 ), indicating that 2 extrudes LiCl at elevated temperatures. Additionally, LiCl in 2 was displaced by reaction with PMe 3, quinuclidine, and dmap (dmap = 4-(dimethylamino)pyridine), providing [(η 3 -allyl TMS2 )Mn{C(SiMe 3 ) 3 }(L)] (L = PMe 3 ( 4 ), quinuclidine ( 5 ), dmap ( 6 )). Treatment of PMe 3 complex 4 with BPh 3 yielded bright red [(allyl TMS2 )Mn{C(SiMe 3 ) 3 }] ( 7 ) accompanied by a precipitate of Ph 3 B(PMe 3 ). Mixed alkyl/π-allyl manganese(II) complexes 2 – 7 are pyrophoric red solids with a high-spin d 5 configuration, and all were crystallographically characterized. In the solid-state structures, the allyl ligands in 2 – 6 adopt a syn, syn configuration, whereas in base-free 7, the allyl ligand has a syn, anti configuration. Complexes 4, 5, and 7 sublimed cleanly (5 mTorr) at 70, 90, and 50 °C, respectively. Complex 4 exhibited a particularly favorable combination of volatility and thermal stability, given that its appearance and powder X-ray diffraction pattern were unchanged after 24 h in a sealed flask at 100 °C. Compounds 2 – 7 are the first high-spin d 5 mixed alkyl/allyl complexes, and 7 is the first room-temperature-stable example of a mononuclear transition-metal complex bearing only alkyl and allyl ligands.
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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) | 0.002 | 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".