Elucidation of the Formation Mechanisms of the Octahydrotriborate Anion (B3H8–) through the Nucleophilicity of the B–H Bond
| Autor: | Qian-Fan Zhang, Xi-Meng Chen, Nana Ma, Changgeng Wei, Xuenian Chen, Jin Wang, Jie Zhang, Xiaoge Feng, Lai-Sheng Wang |
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| Rok vydání: | 2018 |
| Předmět: |
010405 organic chemistry
Chemistry Hydrogen bond chemistry.chemical_element General Chemistry 010402 general chemistry 01 natural sciences Biochemistry Medicinal chemistry Catalysis 0104 chemical sciences Ion Colloid and Surface Chemistry Nucleophile Yield (chemistry) Electrophile Nucleophilic substitution Boron |
| Zdroj: | Journal of the American Chemical Society. 140:6718-6726 |
| ISSN: | 1520-5126 0002-7863 |
| Popis: | Boron compounds are well-known electrophiles. Much less known are their nucleophilic properties. By recognition of the nucleophilicity of the B–H bond, the formation mechanism of octahydrotriborate (B3H8–) was elucidated on the bases of both experimental and computational investigations. Two possible routes from the reaction of BH4– and THF·BH3 to B3H8– were proposed, both involving the B2H6 and BH4– intermediates. The two pathways consist of a set of complicated intermediates, which can convert to each other reversibly at room temperature and can be represented by a reaction circle. Only under reflux can the B2H6 and BH4– intermediates be converted to B2H5– and BH3(H2) via a high energy barrier, from which H2 elimination occurs to yield the B3H8– final product. The formation of B2H6 from THF·BH3 by nucleophilic substitution of the B–H bond was captured and identified, and the reaction of B2H6 with BH4– to produce B3H8– was confirmed experimentally. On the bases of the formation mechanisms of B3H8–, we ha... |
| Databáze: | OpenAIRE |
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