The Chemistry of Low Valent Organosamarium(II) Complexes

最近几年合成的最有趣的新型有机金属化合物是本研究项目正在研究的金属钐化合物。这些化合物在向其他分子中添加电子方面是非常强大的试剂，在这方面可以与非常活跃的金属钠相媲美，但与钠相比，它们的优点是可溶于各种有机溶剂。首席研究员已经使用这些钐化合物来实现小分子的各种不同寻常的转化，这些试剂有望在复杂有机分子的新合成开发中发挥重要作用。本研究的目标是：(1)充分定义有机金属Sm（II）配合物的反应性；(2)在(a)小分子的不寻常转化中利用这种反应性；(b)复杂有机分子的新合成；(c)不寻常无机材料的开发；以及(d)提高对有机金属化学的总体理解。这些目标将通过详细研究双（五甲基环戊二烯）-钐（II）的双- thf加合物对CO、炔烃、RN=NR和异腈的活化来实现；同时探索该试剂如何激活腈、亚胺、NO和二氧化碳；通过适当的反应性研究来研究双-(Cp*)Sm（II）不寻常的弯曲结构；比较了双-(Cp*)Sm（II）及其双- thf加合物的化学性质；通过研究有机钐（II）配合物与无机底物的反应性；并通过探索新的Ln（II）物种。

Among the most interesting new organometallic compounds to be synthesized in the last several years are the compounds of the metal samarium which are the under study in this research project. These compounds are very powerful reagents for the addition of electrons to other molecules, rivalling the very reactive metal sodium in their ability to so, but having the advantage over sodium of being soluble in a variety of organic solvents. The Principal Investigator has used these samarium compounds to bring about a wide variety of unusual transformations of small molecules, and these reagents are expected to be valuable in the development of new syntheses of complex organic molecules. The objectives of this investigation are (1) to define fully the reactivity of organometallic Sm(II) complexes and (2) to exploit this reactivity in (a) unusual transformations of small molecules, (b) new syntheses of complex organic molecules, (c) the development of unusual inorganic materials, and (d) the enhancement of understanding of organometallic chemistry in general. These objectives will be accomplished by studying in detail the activation of CO, alkynes, RN=NR, and isonitriles by the bis-THF adduct of bis(pentamethylcyclopentadienide)- samarium(II); by also exploring how this reagent activates nitriles, imides, NO and carbon dioxide; by investigating the unusual bent structure of bis-(Cp*)Sm(II) with appropriate reactivity studies; by contrasting the chemistry of bis-(Cp*)Sm(II) and of its bis-THF adduct; by investigating the reactivity of organosamarium(II) complexes with inorganic substrates; and by exploring new types of Ln(II) species.