Transition Metal-Catalyzed Formation of Boron−Nitrogen Bonds: Catalytic Dehydrocoupling of Amine-Borane Adducts to Form Aminoboranes and Borazines
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Bibliographic record
Abstract
A mild, catalytic dehydrocoupling route to aminoboranes and borazine derivatives from either primary or secondary amine-borane adducts has been developed using late transition metal complexes as precatalysts. The adduct Me(2)NH.BH(3) thermally eliminates hydrogen at 130 degrees C in the condensed phase to afford [Me(2)N-BH(2)](2) (1). Evidence for an intermolecular process, rather than an intramolecular reaction to form Me(2)N=BH(2) as an intermediate, was forthcoming from "hot tube" experiments where no appreciable dehydrocoupling of gaseous Me(2)NH.BH(3) was detected in the range 150-450 degrees C. The dehydrocoupling of Me(2)NH.BH(3) was found to be catalyzed by 0.5 mol % [Rh(1,5-cod)(mu-Cl)](2) in solution at 25 degrees C to give 1 quantitatively after ca. 8 h. The rate of dehydrocoupling was significantly enhanced if the temperature was raised or if the catalyst loading was increased. The catalytic activity of various other transition metal complexes (Ir, Ru, Pd) for the dehydrocoupling of Me(2)NH.BH(3) was also demonstrated. This new catalytic method was extended to other secondary adducts RR'NH.BH(3) which afforded the dimeric species [(1,4-C(4)H(8))N-BH(2)](2) (2) and [PhCH(2)(Me)N-BH(2)](2) (3) or the monomeric aminoborane (i)Pr(2)N=BH(2) (4) under mild conditions. A new synthetic approach to the linear compounds R(2)NH-BH(2)-NR(2)-BH(3) (5: R = Me; 6: R = 1,4-C(4)H(8)) was developed and subsequent catalytic dehydrocoupling of these species yielded the cyclics 1 and 2. The species 5 and 6 are postulated to be intermediates in the formation of 1 and 2 directly from the catalytic dehydrocoupling of the adducts R(2)NH.BH(3). The catalytic dehydrocoupling of NH(3).BH(3), MeNH(2).BH(3), and PhNH(2).BH(3) at 45 degrees C to give the borazine derivatives [RN-BH](3) (10: R = H; 11: R = Me; 12: R = Ph) was demonstrated. TEM analysis of the contents of the reaction solution for the [Rh(1,5-cod)(mu-Cl)](2) catalyzed dehydrocoupling of Me(2)NH.BH(3) together with Hg poisoning experiments suggested a heterogeneous catalytic process involving Rh(0) colloids.
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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) | 0.000 | 0.000 |
| 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 | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.000 | 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