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.

过渡金属配合物的刘易斯碱性构成了无机化学和催化的基础，但是，基于过渡金属刘易斯基地的刘易斯加合物的明确实例仍然非常罕见。该提案要求续签我们以前的DFG赠款（2011-2014）与主要群体和过渡金属之间的纽带有关，在此期间，我们详细介绍了仅金属刘易斯对（MOLPS）的概念。该项目见证了刘易斯碱基和适合形成molps，许多边界案例以及在某些情况下异常替代反应结果的范围的显着扩展。 MOLP反应性的范围也大大扩大。本文提出的未来工作采取了两个不同的方向。亚参数A：新的刘易斯酸和碱成分的发展，它们的组合形成摩尔普，以及进一步的反应性和光谱研究，以更好地理解金属对元素的键合键的性质。亚参数B：将动态金属对元素的键用作超分子化学的结构元素，这是该领域从未使用过的一种键。该亚项目旨在首先开发出多次刘易斯酸和基础构建块的合成途径，并结合起来构建原则上分子的验证。

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

Steric Control between Neutral Metal-Only Lewis Pairs and Metal-Stabilized Gallenium and Gallinium Cations

仅中性金属的路易斯对与金属稳定的镓和镓阳离子之间的空间控制

• DOI: 10.1021/acs.organomet.6b00045
• 发表时间: 2016
• 期刊: Organometallics
• 影响因子: 2.8
• 作者: H. Braunschweig;R. D. Dewhurst;C. Schneider
• 通讯作者: C. Schneider