Preparation, characterization and study of the reactivity of high energy intermediates formed in metal-atom reactions

活性金属对有机合成产生了重大影响。此外，许多工业上重要的过程都使用金属作为催化剂。这些过程的效率取决于金属的性质、载体上的材料以及将金属引入载体中的可用技术。我的研究项目涉及研究金属原子的反应，目的是了解金属介导的催化的控制机制，表面化学和有机金属化合物的形成。金属原子将在-196摄氏度的高真空室中与有机化合物反应，该真空室被称为旋转低温恒温器。金属原子反应中产生的金属丝或颗粒将被用来产生金属原子。金属原子反应中产生的产物的特殊之处在于它们的不稳定性使它们具有非凡的反应活性。我们将利用这些化合物的不同寻常的反应活性，在-196摄氏度和室温之间用适当的反应剂处理它们，以提供反应速度、产品产率和成本效率更高的新合成路线。由含有金属原子的环状化合物，即金属环，是许多催化过程中涉及的重要中间体。我们将研究这些中间体是如何形成的，以及它们与含有缺电子中心的化合物反应的能力。此外，为了更好地了解催化过程，我们将研究在一些不同的金属原子反应中形成的有机金属中间体的性质。为了做到这一点，我们将收集中间体并通过电子顺磁共振(EPR)光谱技术确定其结构。从光谱中提取的参数将为我们提供有关反应中产生的金属中心自由基的成键特征的信息。我们将研究的一些系统包括有机锰中间体、在Y原子反应中形成的中间体以及零价铜的有机金属络合物。

Activated metals have had a significant impact on organic synthesis.  Also, many industrially important processes use metals as catalysts.  The efficiency of the processes depends on the nature of the metal, the material on which it is supported and the techniques available to introduce the metal into the support.  My research program involves studying the reactions of metal atoms with the aim of understanding the mechanisms controlling metal mediated catalysis, surface chemistry and the formation of organometallic compounds.  Metal atoms will be reacted with organic compounds at -196 degrees Celsius in a high vacuum chamber called a 'rotating cryostat'.  Pieces of metal wire or pellets heated in a furnace will be used to generate the metal atoms.  The products generated in the metal atom reactions are special in that their instability affords them extraordinary reactivity.  We will take advantage of the unusual reactivity of these compounds by treating them with appropriate reactants between -196 degrees Celsius and room temperature to provide new synthetic routes with increased reaction rates, product yield and cost efficiency.  Cyclic compounds containing a metal atom, i.e., metallacycles, are important intermediates implicated in many catalytic processes.  We will study how these intermediates are formed as well as their ability to react with compounds containing electron-deficient centres.  In addition, to gaining a better understanding of catalytic processes, we will investigate the nature of the organometallic intermediates formed in a number of different metal atom reactions.  To do this the intermediates will be collected and their structure determined by a spectroscopic technique known as electron paramagnetic resonance (EPR) spectroscopy.  The parameters extracted from the spectra will give us information about the bonding characteristics of metal-centered radicals generated in our reactions.  Some of the systems we will investigate include organomagnanese intermediates, intermediates formed in yttrium atom reactions and organometallic complexes of zerovalent copper.