Elucidation of the Reaction Mechanisms of Hydrosilylations with Cationic Transition-Metal Catalysts

阳离子过渡金属催化剂氢化硅烷化反应机理的阐明

基本信息

  • 批准号:
    427411484
  • 负责人:
  • 金额:
    --
  • 依托单位:
  • 依托单位国家:
    德国
  • 项目类别:
    Research Grants
  • 财政年份:
    2019
  • 资助国家:
    德国
  • 起止时间:
    2018-12-31 至 2022-12-31
  • 项目状态:
    已结题

项目摘要

The mechanistic understanding of chemical reactions is a fundamental requirement for their further development. We have been engaged for quite a while in the experimental elucidation of the ionic hydrosilylation of carbonyl compounds catalyzed by main-group Lewis acids and transition-metal complexes, respectively. The key insight of our preliminary work is that those hydrosilylation reactions that are promoted by cationic transition-metal catalysts do not proceed by their postulated reaction mechanisms. Our laboratory showed for two prominent cases that the neutral transition-metal hydride formed as an intermediate during the catalysis is not sufficiently hydridic to reduce the silylcarboxonium ion. Another molecule of the hydrosilane is needed to activate that transition-metal hydride either by coordination or even oxidative addition of the Si‒H bond (two-silicon rather than one-silicon cycle). Hence, more than one equivalent of the hydrosilane is required to accelerate and drive these hydrosilylations to completion. The consequences of this finding are far-reaching as it means that reported mechanisms of related hydrosilylation reactions are also likely to require partial revision. Within this project, we verify the generality of our hypothesis by systematically looking into the mechanisms of two additional representative carbonyl hydrosilylations. We hope that a universally valid mechanistic picture will evolve from this.
对化学反应机理的理解是其进一步发展的基本要求。我们一直致力于主族刘易斯酸和过渡金属配合物催化羰基化合物离子硅氢化反应的实验研究。我们的初步工作的关键见解是,这些硅氢加成反应,促进了阳离子过渡金属催化剂不进行其假定的反应机理。我们的实验室在两个突出的例子中表明,在催化过程中作为中间体形成的中性过渡金属氢化物不足以还原甲硅烷基碳鎓离子。需要另一个氢硅烷分子来活化过渡金属氢化物,通过配位或甚至氧化添加Si-OH键(两个硅而不是一个硅环)。因此,需要多于一当量的氢硅烷来加速和驱动这些氢化硅烷化完成。这一发现的后果是深远的,因为它意味着相关氢化硅烷化反应的报告机制也可能需要部分修订。在这个项目中,我们验证了我们的假设的一般性,通过系统地研究两个额外的代表性羰基硅氢化的机制。我们希望,一个普遍有效的机械图将由此演变。

项目成果

期刊论文数量(0)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)

数据更新时间:{{ journalArticles.updateTime }}

{{ item.title }}
{{ item.translation_title }}
  • DOI:
    {{ item.doi }}
  • 发表时间:
    {{ item.publish_year }}
  • 期刊:
  • 影响因子:
    {{ item.factor }}
  • 作者:
    {{ item.authors }}
  • 通讯作者:
    {{ item.author }}

数据更新时间:{{ journalArticles.updateTime }}

{{ item.title }}
  • 作者:
    {{ item.author }}

数据更新时间:{{ monograph.updateTime }}

{{ item.title }}
  • 作者:
    {{ item.author }}

数据更新时间:{{ sciAawards.updateTime }}

{{ item.title }}
  • 作者:
    {{ item.author }}

数据更新时间:{{ conferencePapers.updateTime }}

{{ item.title }}
  • 作者:
    {{ item.author }}

数据更新时间:{{ patent.updateTime }}

Professor Dr. Martin Oestreich其他文献

Professor Dr. Martin Oestreich的其他文献

{{ item.title }}
{{ item.translation_title }}
  • DOI:
    {{ item.doi }}
  • 发表时间:
    {{ item.publish_year }}
  • 期刊:
  • 影响因子:
    {{ item.factor }}
  • 作者:
    {{ item.authors }}
  • 通讯作者:
    {{ item.author }}

{{ truncateString('Professor Dr. Martin Oestreich', 18)}}的其他基金

Transition-Metal-Free Transfer Hydrohalogenation
无过渡金属转移氢卤化
  • 批准号:
    405628012
  • 财政年份:
    2018
  • 资助金额:
    --
  • 项目类别:
    Research Grants
Ionic and Radical Cross-Couplings for Carbon-Silicon Bond Formation
碳-硅键形成的离子和自由基交叉偶联
  • 批准号:
    388910461
  • 财政年份:
    2017
  • 资助金额:
    --
  • 项目类别:
    Research Grants
Enantioselective Silylation of Simple Alcohols by Catalyst-Controlled Dehydrogenative Si-O Coupling
催化剂控制的脱氢 Si-O 偶联对简单醇进行对映选择性硅烷化
  • 批准号:
    388204995
  • 财政年份:
    2017
  • 资助金额:
    --
  • 项目类别:
    Research Grants
Chiral Sulfur-Stabilized Silicon Cations as Lewis Acids for Enantioselective Diels-Alder Reactions
手性硫稳定硅阳离子作为路易斯酸用于对映选择性狄尔斯-阿尔德反应
  • 批准号:
    287280002
  • 财政年份:
    2015
  • 资助金额:
    --
  • 项目类别:
    Research Grants
Catalytic enantioselective hydrosilylation of pyridines and benzannulated congeners
吡啶和苯环化同系物的催化对映选择性氢化硅烷化
  • 批准号:
    250883966
  • 财政年份:
    2014
  • 资助金额:
    --
  • 项目类别:
    Research Grants
3-Silylated Cyclohexa-1,4-dienes as Surrogates for Gaseous and Harmful Hydrosilanes in Lewis-Acid Catalysis
3-硅烷化环六-1,4-二烯作为路易斯酸催化中气态和有害氢硅烷的替代品
  • 批准号:
    255836950
  • 财政年份:
    2014
  • 资助金额:
    --
  • 项目类别:
    Research Grants
Erzeugung und Charakterisierung neuartiger übergangsmetallstabilisierter Silyliumionen
新型过渡金属稳定硅离子的生成和表征
  • 批准号:
    223669596
  • 财政年份:
    2012
  • 资助金额:
    --
  • 项目类别:
    Research Grants
Kooperative Si-H-Bindungsaktivierung: Erzeugung potenter Siliciumelektrophile für die katalytische C(sp3)-F-Bindungsaktivierung
协同 Si-H 键活化:生成有效的硅亲电子试剂,用于催化 C(sp3)-F 键活化
  • 批准号:
    218347001
  • 财政年份:
    2012
  • 资助金额:
    --
  • 项目类别:
    Research Grants
Zinc Atom Transfer-Based Silylzincation of Alkynes
基于锌原子转移的炔烃的甲硅烷基锌化
  • 批准号:
    208581294
  • 财政年份:
    2012
  • 资助金额:
    --
  • 项目类别:
    Research Grants
Heterolytische Aktivierung von H-H- und Si-H-Bindungen durch Lewis-Säure-/Lewis-Base-Paare in (asymmetrischen) metallfreien Reduktionen
在(不对称)无金属还原中路易斯酸/路易斯碱对对 H-H 和 Si-H 键的杂解活化
  • 批准号:
    105045747
  • 财政年份:
    2008
  • 资助金额:
    --
  • 项目类别:
    Research Grants

相似国自然基金

Exploring the Intrinsic Mechanisms of CEO Turnover and Market Reaction: An Explanation Based on Information Asymmetry
  • 批准号:
    W2433169
  • 批准年份:
    2024
  • 资助金额:
    万元
  • 项目类别:
    外国学者研究基金项目
基于Hydrodynamics-Reaction Kinetics耦合模型的厌氧膨胀床反应器三相流场数值模拟及生态-水力响应机制解析
  • 批准号:
    51078108
  • 批准年份:
    2010
  • 资助金额:
    36.0 万元
  • 项目类别:
    面上项目

相似海外基金

Elucidation of reaction mechanisms at gas-liquid interfaces in the atmosphere
阐明大气中气液界面的反应机制
  • 批准号:
    19H01154
  • 财政年份:
    2019
  • 资助金额:
    --
  • 项目类别:
    Grant-in-Aid for Scientific Research (A)
Elucidation of proton generation and transport mechanisms in catalytic reaction of [NiFe] hydrogenase
阐明[NiFe]氢化酶催化反应中质子的产生和传输机制
  • 批准号:
    18K05318
  • 财政年份:
    2018
  • 资助金额:
    --
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Elucidation of Reactivity and Reaction Mechanisms of Gas-phase Multi-elemental Clusters under Thermal Conditions
热条件下气相多元素团簇的反应活性和反应机制的阐明
  • 批准号:
    17K14433
  • 财政年份:
    2017
  • 资助金额:
    --
  • 项目类别:
    Grant-in-Aid for Young Scientists (B)
Search for enzymes that introduce a triple bond between two carbon atoms and elucidation of their reaction mechanisms
寻找在两个碳原子之间引入三键的酶并阐明其反应机制
  • 批准号:
    16K14898
  • 财政年份:
    2016
  • 资助金额:
    --
  • 项目类别:
    Grant-in-Aid for Challenging Exploratory Research
For discovery of new drugs; elucidation of correlation between reaction mechanisms and structural features in Ngb/Cgb
用于发现新药;
  • 批准号:
    26860022
  • 财政年份:
    2014
  • 资助金额:
    --
  • 项目类别:
    Grant-in-Aid for Young Scientists (B)
Theoretical elucidation on the full reaction mechanisms of threonine synthase
苏氨酸合酶全反应机制的理论阐明
  • 批准号:
    26410002
  • 财政年份:
    2014
  • 资助金额:
    --
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Elucidation of succinyl transferase reaction mechanisms which is difficult to perform by organic synthesis
阐明有机合成难以实现的琥珀酰转移酶反应机制
  • 批准号:
    23710277
  • 财政年份:
    2011
  • 资助金额:
    --
  • 项目类别:
    Grant-in-Aid for Young Scientists (B)
Development of Automated Reaction Path Search Methods for Systematic Elucidation of Enzymatic Reaction Mechanisms
开发自动反应路径搜索方法以系统阐明酶反应机制
  • 批准号:
    23685004
  • 财政年份:
    2011
  • 资助金额:
    --
  • 项目类别:
    Grant-in-Aid for Young Scientists (A)
Elucidation of redox reaction mechanisms and control of oxidation states of actinide ions in a neutral solution or dispersed solution
阐明氧化还原反应机制以及控制中性溶液或分散溶液中锕系离子的氧化态
  • 批准号:
    22560832
  • 财政年份:
    2010
  • 资助金额:
    --
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Elucidation of the reaction mechanisms for mitochondrial respiratory complex I
线粒体呼吸复合物 I 反应机制的阐明
  • 批准号:
    22570122
  • 财政年份:
    2010
  • 资助金额:
    --
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
{{ showInfoDetail.title }}

作者:{{ showInfoDetail.author }}

知道了