Acetate assisted C-H activation: A computational and experimental study

乙酸辅助 C-H 活化：计算和实验研究

• 批准号: EP/D055016/1
• 负责人: Stuart Macgregor
• 金额: $ 11.93万
• 依托单位: Heriot-Watt University
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2006
• 资助国家: 英国
• 起止时间: 2006 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FD055016%2F1
• 关键词: Acetate; assisted; activation; computational; experimental

A huge variety of complex organic molecules are important in a wide range of everyday applications - from pharmaceuticals to plastics. In general the synthesis of these molecules is achieved from somewhat simpler starting materials. A key feature of such startng materials is the presence of a reactive functional group. Often this will be a halogenated group, such as a C-Cl bond. However, the formation of such functional groups is often inefficient and generates environmentally damaging waste - in this case chlorinated waste.In principle, an ideal functional group would be a C-H bond. Starting materials containing C-H bonds are abundant and extremely cheap and so do not require any wasteful prior manipulation. Unfortunately, C-H bonds have one huge drawback - they are generally extremely unreactive. However, we have discovered a way to enhance the reactivity of C-H bonds by using certain metal complexes in combination with a particular base, acetate. Preliminary studies suggest that a positively charged metal can attack a C-H bond and make it susceptible to cleavage by acetate. The result of this process is to 'activate' the C-H bond by making a new metal-carbon bond. Once formed, metal-carbon bonds are very reactive and undergo a wide range of selective transformations, including the formation of C-C bonds that will allow the synthesis of more complicated organic molecules. A catalytic process based on our new metal-promoted C-H activation coupled followed by C-C bond formation would be extremely attractive as it is both extremely efficient (avoids wasteful formation of other reactive functional groups) and environmentally friendly (avoids the formation of byproducts). In our proposed work we aim to understand the fundamental chemistry that lies behind our observation of easy C-H bond activation. We shall use both computational modelling and experimental chemistry to investigate precisely what factors promote this process. Once identified these factors can be included in the design of new catalysts for C-H activation.

各种各样的复杂有机分子在从药品到塑料的各种日常应用中都很重要。一般来说，这些分子的合成是从稍微简单的起始材料实现的。这种起始材料的一个关键特征是存在反应性官能团。通常，这将是卤代基团，例如 C-Cl 键。然而，此类官能团的形成通常效率低下，并且会产生对环境有害的废物 - 在这种情况下是氯化废物。原则上，理想的官能团是 C-H 键。含有C-H键的起始材料丰富且极其便宜，因此不需要任何浪费的预先操作。不幸的是，C-H 债券有一个巨大的缺点——它们通常极不活跃。然而，我们发现了一种通过使用某些金属络合物与特定碱乙酸盐结合来增强 C-H 键反应性的方法。初步研究表明，带正电的金属可以攻击 C-H 键，使其容易被乙酸盐裂解。该过程的结果是通过形成新的金属-碳键来“激活”C-H 键。一旦形成，金属-碳键就非常活跃，并经历广泛的选择性转变，包括形成C-C键，这将允许合成更复杂的有机分子。基于我们新的金属促进的 C-H 活化耦合随后形成 C-C 键的催化过程将非常有吸引力，因为它非常有效（避免浪费地形成其他反应性官能团）并且环境友好（避免副产物的形成）。在我们提出的工作中，我们的目标是了解我们观察到的容易的 C-H 键激活背后的基本化学。我们将使用计算模型和实验化学来精确研究哪些因素促进了这一过程。一旦确定了这些因素，就可以将其纳入用于 C-H 活化的新型催化剂的设计中。

项目成果

Computational and synthetic studies on the cyclometallation reaction of dimethylbenzylamine with [IrCl2Cp*]2: role of the chelating base.

二甲基苄胺与 [IrCl2Cp*]2 环金属化反应的计算和合成研究：螯合碱的作用。

• DOI: http://dx.10.1039/b905469c
• 发表时间: 2009
• 期刊: 2003)
• 作者: Boutadla Y

Computational study of ethene hydroarylation at [Ir(?(2)-OAc)(PMe3)Cp]+.

[Ir(?(2)-OAc)(PMe3)Cp] 乙烯加氢芳基化的计算研究。

• DOI: http://dx.10.1039/c0dt00409j
• 发表时间: 2010
• 期刊: 2003)
• 作者: Davies DL

Alkyl dehydrogenation in a Rh(I) complex via an isolated agostic intermediate.

通过分离的激动中间体在 Rh(I) 络合物中进行烷基脱氢。

• DOI: http://dx.10.1039/b816739g
• 发表时间: 2009
• 期刊: Chemical communications (Cambridge, England)
• 作者: Chaplin AB

Mechanisms of C-H bond activation: rich synergy between computation and experiment.

C-H键激活机制：计算与实验的丰富协同作用。

• DOI: 10.1039/b904967c
• 发表时间: 2009-07-21
• 期刊: Dalton transactions
• 影响因子: 4
• 作者: Youcef Boutadla;D. Davies;S. Macgregor;A. Poblador
• 通讯作者: A. Poblador