Activation of Small Inert Molecules

这项研究项目的目标是利用地球上丰富的氮素和甲烷等小惰性分子和二氧化碳建立化学转化，二氧化碳在大气中的增加是由于人类使用化石燃料引起的，并正在成为全球范围内的严重环境问题。这是以二氧化碳和甲烷为简单碳源，以氮气为简单氮源合成有价值的有机化合物的理想化学过程的基础和基础研究。这些惰性小分子的有效活化和化学利用是化学中最具挑战性的课题之一。本项目的主要成果如下：1)在mi…的作用下，钼钨膦配合物中的氮通过一系列反应转化为吡咯、氨基吡咯等含氮杂环化合物。更多的国际条件。以氮气为原料，用钛系合成了吲哚类化合物。这些结果将开启一种新的固氮化学，其中各种有机氮化合物直接从分子氮中制备。2)二氧化碳在铜电极上的电化学还原导致甲烷、乙烷和乙醇的生成。3)首次以氧化还原酶为电催化剂实现了二氧化碳选择性电化学还原为甲醇。4)二氧化碳在超细铜颗粒修饰的p型硅电极上的光电还原导致甲烷和乙烯的生成比在铜金属电极上更正。5)发展了利用铜催化剂将甲烷和一氧化碳转化为醋酸的新反应。这为甲烷在温和条件下的碳-碳键形成反应提供了第一个例子。较少

The Objective of this research project lines in the establishment of chemical transformaitons using small inert molecules such as dinitrogen and methane which are abundant on earth, and carbon dioxide, the increase of which in the atmosphere arises from the use of fossil fuel by the human being and is becoming a serious environmental problems on a global scale. This is the fundamental and basic research towards the development of ideal chemical processes using carbon dioxide and methane as the simple carbon resourse and dinitrogen as the simple nitrogen resource to synthesize valuable organic compounds.Efficient activation and chemical utilization of these small inert molecules are one of the most challenging subjects in chemistry. The main achievements in this project are described below.1) The coordinated dinitrogen in molybdenum and tungsten phosphine complexes has been converted into nitrogen-heterocyclic compounds such as pyrrole and aminopyrrole via a series of reactions under mi … More ld conditions. Indole derivatives have also been synthesized from dinitrogen by using titanium systems. These results will open a new chemistry of nitrogen fixation where a variety of organo-nitrogen compounds are directly prepared from molecular nitrogen.2) Electrochemical reduction of carbon dioxide on a copper electrode gives rise to the formation of methane, ethane, and ethanol. The reaction has been revealed to proceed through the formaiton of carbon monoxide as an intermediate on the electrode.3) Selective electrochemical reduction of carbon dioxide to methanol has been for the first time realized by using redox enzymes as electrocatalysts.4) Photoelectrochemical reduction of carbon dioxide on the p-type silicon electrode modified with ultrafine copper particles has led to the formation of methane and ethylene at a more positive potential than on a copper metal electrode.5) New reactions have been developed which transform methane and carbon monoxide into acetic acids by using copper catalyst. This provides the first example of the carbon-carbon bond formation reactions of methane under mild conditions. Less