Transition-Metal-Catalysed Borane Dehydrocoupling and its Mechanistic Implications

过渡金属催化硼烷脱氢偶联及其机理意义

• 批准号: 242159665
• 负责人: Professor Dr. Holger Braunschweig
• 金额: --
• 依托单位: Institut für Anorganische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2013
• 资助国家: 德国
• 起止时间: 2012-12-31 至 2016-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/242159665?language=en
• 关键词: Transition; Metal; Catalysed; Borane; Dehydrocoupling

The search for more efficient processes for the preparation of useful materials is perpetual.Thereby, the design of chemical syntheses that limit waste products is a particularly vibrant field of research, and one class of reactions is near the pinnacle of the low-waste ideal: dehydrocoupling. Dehydrocoupling reactions are a way to create bonds between elements by eliminating only hydrogen gas from the mixture. Although not completely waste-free, the by-product H2 is easily removed, can be used for other purposes and is much lighter than the product molecules. Our preliminary work on applying this concept to the synthesis of dibo-ranes(4), reagents widely used in organic synthesis, led to their catalytic synthesis with high efficiency. This proposal aims to expand these results in order to widen the scope of the reaction to different substrates, to use the new reaction to prepare boron-containing polymers with interesting properties, and to investigate the mechanism of the reaction from a molecular viewpoint.

寻找更有效的方法来制备有用材料是永恒的。因此，限制废物的化学合成设计是一个特别充满活力的研究领域，并且一类反应接近低废物理想的顶峰：脱氢偶联。脱氢偶联反应是一种通过仅从混合物中消除氢气来在元素之间形成键的方法。虽然并非完全无废物，但副产物 H2 很容易去除，可用于其他目的，并且比产物分子轻得多。我们的初步工作是将这一概念应用于有机合成中广泛使用的试剂二硼烷(4)的合成，从而实现了高效的催化合成。该提案旨在扩展这些结果，以扩大反应范围到不同的底物，利用新的反应制备具有有趣性能的含硼聚合物，并从分子角度研究反应机理。

项目成果

Unprecedented Borane, Diborane(3), Diborene, and Borylene Ligands via Pt-Mediated Borane Dehydrogenation.

通过铂介导的硼烷脱氢获得前所未有的硼烷、乙硼烷(3)、二硼烯和硼烯配体

• DOI: 10.1021/jacs.5b11315
• 发表时间: 2016
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: N. Arnold; H. Braunschweig; R. D. Dewhurst; W. C. Ewing
• 通讯作者: W. C. Ewing

Correlations and Contrasts in Homo- and Heteroleptic Cyclic (Alkyl)(amino)carbene-Containing Pt(0) Complexes.

含 Pt(0) 配合物的均配和杂配环（烷基）（氨基）卡宾的相关性和对比

• DOI: 10.1002/chem.201502048
• 发表时间: 2015
• 期刊: Chemistry
• 作者: N. Arnold; H. Braunschweig; P. B. Brenner; M. A. Celik; R. D. Dewhurst; M. Haehnel; T. Kramer; I. Krummenacher; T. B. Marder
• 通讯作者: T. B. Marder

Aryldihydroborane Coordination to Iridium and Osmium Hydrido Complexes

芳基二氢硼烷与铱和锇氢配合物的配位

• DOI: 10.1021/acs.organomet.5b00788
• 发表时间: 2015
• 期刊: Organometallics
• 影响因子: 2.8
• 作者: N. Arnold; S. Mozo; U. Paul; U. Radius; H. Braunschweig
• 通讯作者: H. Braunschweig

Building Electron‐Precise BoronBoron Single Bonds: Imposing Monogamy on a Promiscuous Element

构建电子——精确的硼单键：在混杂元素上实施一夫一妻制

• DOI: 10.1002/cctc.201500219
• 发表时间: 2015-06-01
• 期刊: ChemCatChem
• 影响因子: 4.5
• 作者: H. Braunschweig;Rian D. Dewhurst;Silvia Mozo
• 通讯作者: Silvia Mozo

Formation and Reactivity of Electron-Precise B-B Single and Multiple Bonds.

电子精确 B-B 单键和多重键的形成和反应性。

• DOI: 10.1002/anie.201610072
• 发表时间: 2017-01-02
• 期刊: Angewandte Chemie
• 作者: Merle Arrowsmith;H. Braunschweig;Tom E. Stennett
• 通讯作者: Tom E. Stennett