Boron-hydrogen complex models

Examine the electrostatic potential map of H3B THE (borane-tetrahydrofuran complex) on Learning By Modeling How does the electrostatic potential of the hydrogens bonded to boron dif fer from the potential of the hydrogens of the tetrahydrofuran ring" ... 

Bech Nielsen et al. (1988) also made a channeling study of the 2H in B-2H complexes that was similar in principle to that just described but differed in details of technique and in some of the conclusions arrived at. Also, they did not investigate the position of the boron atoms. They used Si uniformly doped with a high (1 x 1019 B/cm3) boron concentration, rather than implanted boron. The surface was etched off after hydrogenation, but no SIMS data was presented to confirm the uniform hydrogen concentration assumed. The penetration depth of the H was given as —7000 A. The channeling measurements were performed at 30 K. For analysis of their data Bech Nielsen et al. used the same model, based on the assumption of statistical equilibrium (SE) of the channeled ions, already described in connection with the measurements of implanted deutrium... 

The most commonly accepted model for the hydrogen-acceptor pairs locates H at the BC site (see Fig. 4). This model was originally proposed for the H—B complex on the basis of satisfied bonds to explain the increased resistivity (Pankove et al., 1983), SIMS profiles (Johnson, 1985), and a hydrogen local-mode frequency consistent with a perturbed hydrogen-silicon bond (Pankove et al., 1985 Johnson, 1985 Du et al., 1985). The acceptor deactivation by atomic hydrogen was subsequently observed for Al, Ga, and In acceptors in silicon (Pankove et al., 1984). Hydrogen local-mode vibrations were identified as well for the H—Al and H—Ga complexes (Stavola et al., 1987). The boron vibrational frequency for the H—B pair was first identified by Stutzmann (1987) and Herrero and Stutzmann (1988a). 

The high stereopreference was rationalized by considering complex 388 in which an attractive n-n donor-acceptor interaction favors co-ordination of the dienophile to the face of the boron center which is cis to the 2-hydroxyphenyl substituent. Hydrogen bonding of the hydroxyl proton of the 2-hydroxyphenyl group to an oxygen of the adjacent B—O bond played an important role in the asymmetric induction. Protection of this hydroxy functionality with a benzyl group caused reversal of enantioselectivity in the cycloaddition of cyclopentadiene with methacrolein (model 389)244. 

If similar processes could be developed at energy conversion efficiency levels that are comparable to the present day SMR-based NH3 synthesis plants, then it would be possible to realize a major reduction in the production costs of ammonia-borane complex. We note that a concept similar to that discussed above has already been developed for nitric acid synthesis process based on boron nitride analogous to the Haber-Bosch route for nitric acid production from NH3. Finally, recent results have shown that unusual parallel behavior exists between hydrocarbons and their corresponding B-N analogues. Thus, hydrogenation of benzene to cyclohexane may also provide a model for the reformation of borazine to other amine-boranes. 

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