Heterolytic Cleavage of Disulfides by Frustrated Lewis Pairs
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Bibliographic record
Abstract
The addition of diphenyl disulfide (PhSSPh) to tBu(2)P(C(6)F(4))B(C(6)F(5))(2) (1) affords the zwitterionic phosphonium borate [tBu(2)P(SPh)(C(6)F(4))B(SPh)(C(6)F(5))(2)] (2), while the addition of a base or donor solvent to 2 effected the liberation of disulfide and the formation of [tBu(2)P(C(6)F(4))B(donor)(C(6)F(5))(2)]. The reaction of 1 with S(8) gave tBu(2)P(S)(C(6)F(4))B(C(6)F(5))(2) (3). In a similar fashion, the frustrated Lewis pair of tBu(3)P/B(C(6)F(5))(3) reacts with RSSR to give [tBu(3)P(SR)][(RS)B(C(6)F(5))(3)] (R = Ph (4), p-tolyl (5), iPr (6)). In contrast, the corresponding reaction of BnSSBn yields a 1:1:1 mixture of tBu(3)P horizontal lineS, Bn(2)S, and B(C(6)F(5))(3). Species 4 reacts with p-tolylSSp-tolyl to give a mixture of 4, 5, PhSSPh, and p-tolylSS p-tolyl, while treatment of 5 with PhSSPh afforded a similar mixture. To probe this, a crossover experiment between [tBu(3)P(SPh)][B(C(6)F(5))(4)] (7) and [NBu(4)][(p-tolylS)B(C(6)F(5))(3)] (9) was performed. The former species was prepared by a reaction of 4 with [Ph(3)C][B(C(6)F(5)) (4)], while cation exchange of [(Et(2)O)(2)Li( p-tolylS)B(C(6)F(5))(3)] (8) with [NBu(4)]Br gave 9. The reaction of compounds 7 and 9 gave a statistical mixture of the cations [tBu(3)P(SR)](+) and anions [(RS)B(C(6)F(5))(3)](-), R = Ph, Sp-tolyl. The mechanism of this exchange process was probed and is proposed to be an equilibrium involving disulfide and the frustrated Lewis pair. Crystallographic data are reported for compounds 4-8, and the natures of the P-S cations are examined via DFT calculations.
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Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 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 | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.008 | 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 it