Frustrated Lewis Pair Behavior of Intermolecular Amine/B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub> Pairs
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Bibliographic record
Abstract
Reactions of N, N -dimethylaniline, N- isopropylaniline, 1,4-C 6 H 4 (CH 2 NH t Bu) 2, and benzyldimethylamine with the Lewis acid B(C 6 F 5 ) 3 have been studied. In the case of N, N -dimethylaniline the combination of the Lewis acid and base forms an almost completely noninteracting frustrated Lewis pair, while the corresponding reactions of N- isopropylaniline and benzyldimethylamine with B(C 6 F 5 ) 3 afford the adducts (PhNH i Pr)B(C 6 F 5 ) 3 ( 1 ) and PhCH 2 NMe 2 B(C 6 F 5 ) 3 ( 2 ), respectively. 1,4-C 6 H 4 (CH 2 NH t Bu) 2 reacts with 2 equiv of B(C 6 F 5 ) 3 to give rise to an inseparable mixture of the mono- and bis-amine–borane adducts as well as an iminium salt derived from hydride abstraction from a benzylic carbon of the diamine. Subsequent selected reactions of the Lewis acid/base combinations with H 2 afforded [PhNMe 2 H][HB(C 6 F 5 ) 3 ] ( 3 ), [PhCH 2 NMe 2 H][HB(C 6 F 5 ) 3 ] ( 4 ), and [1,4-C 6 H 4 (CH 2 NH 2 t Bu) 2 ][HB(C 6 F 5 ) 3 ] 2 ( 5 ). Reactions with CO 2 gave PhCH 2 NMe 2 CO 2 B(C 6 F 5 ) 3 ( 6 ), [PhN i PrH 2 ][PhN i PrCO 2 B(C 6 F 5 ) 3 ] ( 8 ), [1,4-C 6 H 4 (CH 2 NH 2 t Bu)(CH 2 N t BuCO 2 B(C 6 F 5 ) 3 ] ( 9 ), and [C 5 H 6 Me 4 NMeH] 2 [1,4-C 6 H 4 (CH 2 N t BuCO 2 B(C 6 F 5 ) 3 ) 2 ] ( 10 ). Interestingly, the species 4 also reacts with CO 2 to give [PhCH 2 NMe 2 H][HCO 2 B(C 6 F 5 ) 3 ] ( 7 ). Species 8 reacts with HSiEt 3 to yield [PhN i PrC(OSiEt 3 )OB(C 6 F 5 ) 3 ] ( 11 ). The adduct 2 also reacts with ethene, 2,4-hexadiyne, and the alkynes HC≡CR (R = n -Bu, Ph, t Bu, SiMe 3 ) to give the 1,2- addition products PhCH 2 NMe 2 CH 2 CH 2 B(C 6 F 5 ) 3 ( 12 ), PhCH 2 NMe 2 C(CCMe)=CMeB(C 6 F 5 ) 3 ( 13 ), and the ammonium alkynylborate salts [PhCH 2 NMe 2 H][RCCB(C 6 F 5 ) 3 ] (R = n -Bu ( 14a ), Ph ( 14b ), t Bu ( 14c ), SiMe 3 ( 14d )). In contrast, the reaction of 1-hexyne with the Lewis pair PhNMe 2 and B(C 6 F 5 ) 3 affords the trans-1,2-addition product PhNMe 2 C(C 4 H 9 )=CH(B(C 6 F 5 ) 3 ) ( 15 ). This chemistry demonstrates the generality of such FLP chemistry, extending it to N-based Lewis bases and thereby expanding the scope for applications of FLP chemistry.
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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 | 0.000 |
| Meta-epidemiology (narrow) | 0.002 | 0.002 |
| Meta-epidemiology (broad) | 0.002 | 0.001 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.000 | 0.001 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.001 | 0.001 |
| Research integrity | 0.002 | 0.002 |
| Insufficient payload (model declined to judge) | 0.001 | 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 it