Synthesis and Reactivity of [SF<sub>3</sub>]<sup>+</sup> Adducts with Organic Bases
Bibliographic record
Abstract
The 1:1 adduct of [SF 3 ] + with pyridine was obtained from the reaction of SF 4 with [(CH 3 ) 3 Si(NC 5 H 5 )][O 3 SCF 3 ] ([(CH 3 ) 3 Si(py)][OTf]) as the [SF 3 (py)][OTf] salt in near quantitative yields. The analogous reaction of SF 4 with [(CH 3 ) 3 Si(4-NC 5 H 5 N(CH 3 ) 2 )][OTf] ([(CH 3 ) 3 Si(dmap)][OTf]) results in the formation of a small amount of [SF 3 (dmap)][OTf], which was found to undergo facile dismutation to [SF 2 (dmap) 2 ][OTf] 2 and SF 4 as the major products of the reaction. NMR spectroscopic data suggest that [SF 3 (dmap)] + adopts a seesaw structure with DMAP in the equatorial position, which is in contrast to the axial position of pyridine in [SF 3 (py)] + . Quantum chemical calculations show that in the gas-phase the axial isomer of [SF 3 (py)] + is the more stable configuration by 28 kJ mol –1, whereas the axial and equatorial isomers of [SF 3 (dmap)] + were predicted to be essentially isoenergetic with <2 kJ mol –1 difference between the two isomers. The reaction of [SF 3 ][SbF 6 ] with DMAP allowed for the isolation of [SF 2 (dmap) 2 ][SbF 6 ] 2 without any evidence of the monocation. In CH 3 CN solutions, [SF 2 (dmap) 2 ] 2+ was found to undergo further ligand scrambling leading to the precipitation of [SF(dmap) 4 ] 3+ salts. Attempts to form a 1:1 adduct between [SF 3 ] + and OPPh 3 result instead in the deoxofluorination of OPPh 3 forming [FPPh 3 ] + salts.
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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) | 0.003 | 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".