Electrophilic Dinitrogen and Hydrocarbon Activation by Fluoroalkylphosphine Complexes

在这个由无机，生物无机和 有机化学课程，院长M。罗迪克 怀俄明州大学将合成过渡金属 含有全氟烷基叔膦的络合物 配体。这些配体是吸电子的， 配合物的金属和辅助配体电子贫乏， 这将导致一种新的化学反应和新的 活化配位二氮的方法， example.氮的配位和反应性是基础- 在从大气中"固定"氮的过程中， 用于有用的目的，例如生产肥料。的 金属络合物也可用作催化剂， 碳氢键活化，这是一个重要的步骤， 将碳氢化合物，特别是甲烷，转化为更多 有用的燃料如甲醇。 所采用的配体将是1，2-双（二全氟烷基膦基） 乙烷，主要是全氟乙基化合物，以及类似物 膦。由此产生的亲电复合物， 然后将研究配体用于烃活化 和二氮配位。一种这样的复合物形成，甲苯- （二氮）钼（全氟烷基膦），以及各种 类似物，将检查的亲电反应性 配位的双氮与亲核试剂如有机- 锂和氢化物试剂。金属要强调的是 这些研究是铬、钼和钨。这个合成词 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.