Dynamic Metal-to-Element Dative Bonds and their Applications Beyond the Molecule

动态金属与元素配位键及其在分子之外的应用

• 批准号: 192178519
• 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: 2010
• 资助国家: 德国
• 起止时间: 2009-12-31 至 2018-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/192178519?language=en
• 关键词: Dynamic; Metal; Element; Dative; Bonds

The Lewis basicity of transition metal complexes forms a foundation of both inorganic chemistry and catalysis, however, unambiguous examples of Lewis adducts based on transition metal Lewis bases are still very rare. This proposal requests renewal of our previous DFG grant (2011-2014) related to dative bonds between main groups and transition metals, during which we elaborated on the concept of metal-only Lewis pairs (MOLPs). This project witnessed the significant expansion of the range of both Lewis base and acid components suitable for forming MOLPs, a number of borderline cases, and in some cases unusual alternative reaction outcomes. The scope of MOLP reactivity was also considerably widened. The future work proposed herein takes two distinct directions. Subproject A: Development of new Lewis acid and base components, their combination to form MOLPs, and further reactivity and spectroscopic studies to better understand the nature of metal-to-element dative bonds. Subproject B: The use of dynamic metal-to-element dative bonds as structural elements for supramolecular chemistry, a type of bond never before used in this field. This subproject aims to first develop synthetic routes to multitopic Lewis acid and base building blocks, and their combination to construct proof-of-principle supramolecular assemblies.

过渡金属络合物的路易斯碱性构成了无机化学和催化的基础，然而，基于过渡金属路易斯碱的路易斯加合物的明确例子仍然非常罕见。该提案要求更新我们之前与主要基团和过渡金属之间的配位键相关的 DFG 拨款（2011-2014 年），在此期间我们详细阐述了纯金属路易斯对（MOLP）的概念。该项目见证了适合形成 MOLP 的路易斯碱和酸组分范围的显着扩展、许多边缘情况，以及在某些情况下不寻常的替代反应结果。 MOLP 反应的范围也大大拓宽了。本文提出的未来工作有两个不同的方向。子项目 A：开发新的路易斯酸和碱组分，将它们组合形成 MOLP，并进行进一步的反应性和光谱研究，以更好地了解金属与元素配位键的性质。子项目 B：使用动态金属与元素配位键作为超分子化学的结构元素，这是该领域以前从未使用过的一种键。该子项目旨在首先开发多主题路易斯酸和碱构建块的合成路线，及其组合以构建原理验证的超分子组装体。

项目成果

Oxidative addition of arsenic halides to platinum(0).

卤化砷对铂的氧化加成(0)

• DOI: 10.1039/c8dt04995e
• 发表时间: 2019
• 期刊: Dalton transactions
• 影响因子: 4
• 作者: J. H. Müssig;T. E. Stennett;U. Schmidt;R. D. Dewhurst;L. Mailänder;H. Braunschweig
• 通讯作者: H. Braunschweig

Lewis Acid Binding and Transfer as a Versatile Experimental Gauge of the Lewis Basicity of Fe(0) , Ru(0) , and Pt(0) Complexes.

路易斯酸结合和转移作为 Fe(0) 、 Ru(0) 和 Pt(0) 配合物路易斯碱度的多功能实验测量

• DOI: 10.1002/chem.201503536
• 发表时间: 2015
• 期刊: Chemistry
• 作者: H. Braunschweig;C. Brunecker;R. D. Dewhurst;C. Schneider;B. Wennemann
• 通讯作者: B. Wennemann

Metal-Only Lewis Pairs Based on Zerovalent Osmium

• DOI: 10.1021/acs.organomet.6b00495
• 发表时间: 2016-08-08
• 期刊: ORGANOMETALLICS
• 影响因子: 2.8
• 作者: Bissert, Robin;Braunschweig, Holger;Schneider, Christoph
• 通讯作者: Schneider, Christoph

Does Lewis basicity correlate with catalytic performance in zerovalent group 8 complexes?

路易斯碱性与零价第 8 族配合物的催化性能相关吗？

• DOI: 10.1515/znb-2017-0193
• 发表时间: 2018
• 期刊: Zeitschrift für Naturforschung B
• 作者: H. Braunschweig;C. Brunecker;R. D. Dewhurst;C. Schneider
• 通讯作者: C. Schneider

Reactions of Digallanes with p- and d-Block Lewis Bases: Adducts, Bis(gallyl) Complexes, and Naked Ga+ as Ligand.

• DOI: 10.1002/chem.201801471
• 发表时间: 2018-06
• 期刊: Chemistry
• 作者: J. Schuster;Jonas H. Muessig;Rian D. Dewhurst;H. Braunschweig