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A comparative theoretical study of the hydride transfer mechanisms during LiAlH4 and LiBH4 reductions
https://doi.org/10.24517/00010817
https://doi.org/10.24517/00010817d20d641d-9ae9-402e-9684-8336b4a09016
| 名前 / ファイル | ライセンス | アクション |
|---|---|---|
SC-PR-HORI-Y-86.pdf (666.5 kB)
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| Item type | 学術雑誌論文 / Journal Article(1) | |||||
|---|---|---|---|---|---|---|
| 公開日 | 2017-12-05 | |||||
| タイトル | ||||||
| タイトル | A comparative theoretical study of the hydride transfer mechanisms during LiAlH4 and LiBH4 reductions | |||||
| 言語 | en | |||||
| 言語 | ||||||
| 言語 | eng | |||||
| 資源タイプ | ||||||
| 資源タイプ識別子 | http://purl.org/coar/resource_type/c_6501 | |||||
| 資源タイプ | journal article | |||||
| ID登録 | ||||||
| ID登録 | 10.24517/00010817 | |||||
| ID登録タイプ | JaLC | |||||
| 著者 |
Hori, Yuta
× Hori, Yuta× Ida, Tomonori× Mizuno, Motohiro |
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| 著者別表示 |
井田, 朋智
× 井田, 朋智× 水野, 元博 |
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| 提供者所属 | ||||||
| 内容記述タイプ | Other | |||||
| 内容記述 | 金沢大学ナノマテリアル研究所 / 金沢大学理工研究域数物科学系 | |||||
| 書誌情報 |
Computational and Theoretical Chemistry 巻 1076, p. 86-93, 発行日 2016-01-15 |
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| ISSN | ||||||
| 収録物識別子タイプ | ISSN | |||||
| 収録物識別子 | 2210-271X | |||||
| NCID | ||||||
| 収録物識別子タイプ | NCID | |||||
| 収録物識別子 | AA12611200 | |||||
| 出版者 | ||||||
| 出版者 | Elsevier | |||||
| 抄録 | ||||||
| 内容記述タイプ | Abstract | |||||
| 内容記述 | This work examined the hydride transfer processes during the reduction of formaldehyde by LiAlH4 or LiBH4, including investigations of the geometries, solvent effects and charge transfer processes along the reaction coordinate, using density functional theory (DFT). The energy and geometry results demonstrate that the transition state (TS) structure for the LiAlH4-formaldehyde complex is reactant-like, while the structure generated by LiBH4 has a product-like geometry, consistent with the Hammond postulate. From a charge density analysis, we also found that both complexes undergo the same essential hydride transfer mechanism, which consists of: (1) single electron transfer to the carbonyl carbon, (2) formation of a bridge bond (X-H-C; X=Al or B) and (3) hydrogen transfer driven by electron transfer. Subsequently, in a fourth step, a single electron flows through the X-H-C bond during transfer of the hydrogen, such that hydrogen atom or proton-coupled electron transfer occurs. In both systems, the presence of tetrahydrofuran as a solvent affects the structure and energy values during the reaction, but not the charge transfer characteristics. We propose that the rate-determining steps during hydride transfer when employing LiAlH4 and LiBH4 are one electron transfer to the carbonyl carbon and B-H bond dissociation, respectively. © 2015 Elsevier B.V. | |||||
| 内容記述 | ||||||
| 内容記述タイプ | Other | |||||
| 内容記述 | Embargo Period 24 months | |||||
| 権利 | ||||||
| 権利情報 | Copyright © Elsevier (CC-BY NC ND) | |||||
| 著者版フラグ | ||||||
| 出版タイプ | AM | |||||
| 出版タイプResource | http://purl.org/coar/version/c_ab4af688f83e57aa | |||||
| 関連URI | ||||||
| 関連タイプ | isVersionOf | |||||
| 識別子タイプ | DOI | |||||
| 関連識別子 | https://doi.org/10.1016/j.comptc.2015.12.014 | |||||
| 関連URI | ||||||
| 関連タイプ | isIdenticalTo | |||||
| 識別子タイプ | URI | |||||
| 関連識別子 | http://www.elsevier.com/locate/issn/2210271X | |||||
