Synthesis and Reactivity of the Phosphinoboranes R<sub>2</sub>PB(C<sub>6</sub>F<sub>5</sub>)<sub>2</sub>
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Bibliographic record
Abstract
The phosphinoboranes [R(2)PB(C(6)F(5))(2)](2) (R = Et 1, Ph 2) and R(2)PB(C(6)F(5))(2) (R = tBu 3, Cy 4, Mes 5) were synthesized from the reaction of (C(6)F(5))(2)BCl and the corresponding lithium phosphide. The relationships between B-P distance, P pyramidality, and the extent of BP multiple bonding were further explored computationally. Natural Bond Order (NBO) analyses of 3 and 4 showed that the π-bonding highest occupied molecular orbitals (HOMOs) were highly polarized. In addition the Lewis acid-base adducts, R(2)(H)P·B(H)(C(6)F(5))(2) (R = Et 6; Ph 7; tBu 8; Cy 9; Mes 10) were prepared via the reaction of the phosphines R(2)PH with the borane HB(C(6)F(5))(2). Compounds 1 and 2 showed no signs of reaction with H(2); however, reaction of compounds 3 and 4 with H(2) was observed to give 8 and 9. In a related set of reactions compounds 3 and 4 were reacted with H(3)NBH(3) or Me(2)(H)NBH(3) also led to the generation of 8 and 9, respectively. The reaction profile of the reaction of (CF(3))(2)BPR(2) with H(2) was examined computationally and shown to be exothermic. Efforts to effect the reverse reaction, that is, dehydrogenation of adducts 6-10 were unsuccessful. Compound 4 was also shown to react with 4-tert-butylpyridine to give Cy(2)PB(C(6)F(5))(2)(4-tBuC(5)H(4)N) 11 while reactions of 3 and 4 with the Lewis acid BCl(3) gave the dimers (R(2)PBCl(2))(2) (R = tBu 12, Cy 13) and the byproduct ClB(C(6)F(5))(2).
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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 | 0.001 | 0.002 |
| Meta-epidemiology (narrow) | 0.002 | 0.002 |
| Meta-epidemiology (broad) | 0.002 | 0.001 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.001 | 0.002 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.003 | 0.002 |
| Research integrity | 0.003 | 0.004 |
| 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 it