Electrophilic Dinitrogen and Hydrocarbon Activation by Fluoroalkylphosphine Complexes

在这项由无机化学、生物无机化学和金属有机化学计划支持的项目中，怀俄明大学的罗迪克院长将合成含有全氟烷基叔膦配体的过渡金属络合物。例如，这些配体是电子引出的，将使配合物的金属和辅助配体缺乏电子，这将导致一种新的化学反应活性和激活配位氮的新方法。氮素的配位和反应活性是从大气中“固定”氮素以用于化肥生产等有用目的的基础。金属络合物还可能用作碳氢键活化的催化剂，这是将碳氢化合物，特别是甲烷转化为更有用的燃料(如甲醇)的重要一步。所使用的配体将是1，2-双(二全氟烷基膦)乙烷，主要是全氟乙基化合物，以及类似的膦。然后将研究得到的这些配体的亲电络合物的碳氢活化和氮配位。甲苯-(dinitrogen)molybdenum(perfluoroalkylphosphine)，和各种类似物就是这样形成的一个络合物，将被检测配位的氮与亲核试剂，如有机锂和氢化物试剂的亲电反应性。在这些研究中要强调的金属是铬、钼和钨。全氟膦的合成研究将继续进行，目的是寻找更有效的配体。

In this project supported by the Inorganic, Bioinorganic and Organometallic Chemistry Program, Dean M. Roddick of the University of Wyoming will synthesize transition metal complexes which contain perfluoralkyl tertiary phosphine ligands. These ligands are electron withdrawing and will render the metal and ancillary ligands of the complexes electron poor, which will lead to a new kind of chemical reactivity and new approaches to the activation of coordinated dinitrogen, for example. The coordination and reactivity of nitrogen is funda- mental in the process of "fixing" nitrogen from the atmosphere for useful purposes such as the production of fertilizer. The metal complexes may also have applications as catalysts for carbon-hydrogen bond activation, which is an important step in the conversion of hydrocarbons, especially methane, to more useful fuels such as methanol. The ligands employed will be 1,2-bis(diperfluoroalkylphosphino) ethane, primarily the perfluoroethyl compound, and analogous phosphines. The resulting electrophilic complexes of these ligands will then be investigated for hydrocarbon activation and dinitrogen coordination. One such complex formed, toluene- (dinitrogen)molybdenum(perfluoroalkylphosphine), and various analogues, will be examined for the electrophilic reactivity of the coordinated dinitrogen with nucleophiles such as organo- lithium and hydride reagents. The metals to be emphasized in these studies are chromium, molybdenum and tungsten. The syn- thetic studies on the perfluorophosphines will continue with the aim of finding more effective ligands.