Reductive elimination with main-group element compounds: From trihydrides to hydrides

主族元素化合物的还原消除：从三氢化物到氢化物

• 批准号: 314084445
• 负责人: Professor Dr. Lars Wesemann
• 金额: --
• 依托单位: Abteilung für Anorganische und Analytische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2016
• 资助国家: 德国
• 起止时间: 2015-12-31 至 2018-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/314084445?language=en
• 关键词: Reductive; elimination; main; group; element

Reductive elimination with main-group element compounds: From trihydrides to hydrides The reductive elimination is an important reaction in metal organic chemistry. In this project we want to study the reductive elimination of hydrogen from germanium and tin compounds and elaborate this reaction towards the synthesis of new molecules. Through the reaction of Lewis bases like trialkylamines, substituted pyridines or N-heterocyclic carbenes with alkyl or aryl substituted trihydrides (R-EH3, E = Ge, Sn) we synthesize hydrides of divalent germanium and tin [(R-E-H)n] and carbene adducts [R-E-H(L)] thereof. Variation of the stoichiometric ratio of the N-heterocyclic carbene offers the possibility to isolate low valent clusters of type [(RE)n]. Because trihydrides are also known for substituents with less steric demand we aim on studying the steric influence of the substituent on the reactivity of the divalent hydrides and the size of the low valent clusters. In order to explore the reactivity of the hydrides and their carbene adducts, oxidative additions with for example boranes or silanes will be studied. The reactivity of the E-H bond will be investigated in reactions with unsaturated molecules like alkynes or ketones. Since divalent tin hydrides carrying sterically demanding substituents are known to catalyze the hydroboration of aldehydes and ketones, we will investigate the catalytic abilities of the synthesized hydrides of germanium and tin in hydroboration or hydrosilylation reactions. Finally, the coordination chemistry of the divalent hydrides is explored. Donor and acceptor properties of the hydridoylenes are investigated and the conditions for the alpha-elimination of the coordinated element hydride are studied.

主族元素化合物的还原消除反应：从三价到四价还原消除反应是金属有机化学中的一个重要反应。在这个项目中，我们想研究锗和锡化合物中氢的还原消除，并详细阐述这种反应，以合成新的分子。通过刘易斯碱如三烷基胺、取代吡啶或N-杂环卡宾与烷基或芳基取代的三氟甲基（R-EH_3，E = Ge，Sn）反应，合成了二价锗和锡的双金属配合物[（R-E-H）_n]及其卡宾加合物[R-E-H（L）]。N-杂环卡宾的化学计量比的变化提供了分离[（RE）n]型低价簇的可能性。由于三取代基也是已知的取代基与空间需求较少，我们的目标是研究的二价取代基的反应性和低价簇的大小的取代基的空间影响。为了探索碳烯及其卡宾加合物的反应性，将研究与例如硼烷或硅烷的氧化加成。E-H键的反应性将在与不饱和分子如炔或酮的反应中进行研究。由于二价锡化合物带有空间要求高的取代基，已知催化醛和酮的硼氢化反应，我们将研究合成的锗和锡化合物在硼氢化或硅氢化反应中的催化能力。最后，探讨了二价配位化合物的配位化学。研究了邻苯二烯的给体和受体性质，并对配位元素氢化物的α-消除条件进行了研究。

项目成果

Deprotonation of Organogermanium and Organotin Trihydrides.

有机锗和有机锡三氢化物的去质子化

• DOI: 10.1021/acs.inorgchem.9b01822
• 期刊: Inorganic chemistry
• 影响因子: 4.6
• 作者: J.-J. Maudrich;F. Diab;S. Weiß;M. Widemann;T. Dema;K. Eichele;H. Schubert;L. Wesemann
• 通讯作者: L. Wesemann

Reductive Elimination of Hydrogen from Bis(trimethylsilyl)methyltin Trihydride and Mesityltin Trihydride.

• DOI: 10.1002/chem.201605317
• 发表时间: 2017-02
• 期刊: Chemistry
• 作者: Jakob‐Jonathan Maudrich;Christian P. Sindlinger;Frederik S. W. Aicher;K. Eichele;H. Schubert;L. Wesemann

Complete Hydrogen Transfer: Tin Hydride Reactivity toward Adamantylisonitrile and Benzonitrile

• DOI: 10.1021/acs.organomet.8b00207
• 发表时间: 2018-06-11
• 期刊: ORGANOMETALLICS
• 影响因子: 2.8
• 作者: Aicher, Frederik S. W.;Eichele, Klaus;Wesemann, Lars
• 通讯作者: Wesemann, Lars

Cationic Stannylenes: In Situ Generation and NMR Spectroscopic Characterization.

阳离子亚锡：原位生成和 NMR 光谱表征

• DOI: 10.1021/acs.inorgchem.6b02377
• 发表时间: 2017
• 期刊: Inorganic chemistry
• 影响因子: 4.6
• 作者: C. P. Sindlinger;F. S. W. Aicher;L. Wesemann
• 通讯作者: L. Wesemann

Reductive Dehydrogenation of a Stannane via Multiple Sn-H Activation by Frustrated Lewis Pairs.

• DOI: 10.1002/anie.201610254
• 发表时间: 2017-02
• 期刊: Angewandte Chemie
• 作者: Christian P. Sindlinger;Frederik S. W. Aicher;H. Schubert;L. Wesemann