The Chemistry of Low Valent Organosamarium(II) Complexes

在最近几年将要合成的最有趣的新的金属有机化合物中，金属钐的化合物是本研究项目中正在研究的。这些化合物是非常强大的试剂，可以将电子加到其他分子上，在能力上可以与非常活跃的金属钠相媲美，但与钠相比，它们具有在各种有机溶剂中可溶的优势。首席研究员使用这些化合物引起了小分子的各种不寻常的转变，这些试剂有望在复杂有机分子的新合成中发挥重要作用。本研究的目的是(1)充分确定有机金属Sm(II)配合物的反应性，(2)在(A)小分子的异常转化，(B)复杂有机分子的新合成，(C)特殊无机材料的开发，以及(D)加强对一般有机金属化学的理解方面开发这种反应性。这些目标将通过详细研究双(五甲基环戊二烯)-钐(II)的双四氢呋喃加合物对CO、炔烃、RN=NR和异腈的活化来实现，还通过探索该试剂如何激活腈、亚胺、NO和二氧化碳来实现；通过适当的反应性研究来研究双(Cp*)Sm(II)的不寻常的弯曲结构；通过对比双(Cp*)Sm(II)及其双四氢呋喃加合物的化学结构；通过研究有机钼(II)与无机底物的反应性；通过探索新类型的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.