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Lewis碱性构成了无机化学和催化的基础，然而，基于过渡金属Lewis碱的Lewis加合物的明确例子仍然非常罕见。这项提议要求延长我们之前的DFG拨款(2011-2014年)，该拨款涉及主要基团和过渡金属之间的与键，在此期间我们详细阐述了纯金属Lewis对(MOLP)的概念。该项目见证了适合形成MOLP的Lewis碱和酸成分范围的显著扩大，一些临界情况，以及在某些情况下不寻常的替代反应结果。MOLP反应的范围也大大扩大了。这里提出的未来工作有两个截然不同的方向。子项目A：开发新的Lewis酸和碱成分，它们的结合形成MOLP，以及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：在超分子化学中使用动态的金属-元素配位键作为结构元素，这是一种以前从未在该领域中使用过的键。这个子项目的目标是首先开发合成路线，以获得多主题的Lewis酸和碱构建块，并将它们结合起来构建原则证明超分子组件。

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