The Chemistry of Low Valent Organosamarium(II) Complexes

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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.