Expanding Synthetic Aspects Of Redox And Mechanical Organometallic Chemistry Of Rare Earth Complexes

Download or read book Expanding Synthetic Aspects of Redox and Mechanical Organometallic Chemistry of Rare Earth Complexes written by Christopher Matthew Kotyk and published by . This book was released on 2015 with total page 132 pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation describes the synthesis, characterization, and reactivity of organometallic complexes of yttrium and the lanthanides in an effort to more completely understand the nature of a recently-discovered class of +2 ions of these rare earth metals. The reactivity of complexes of a new set of Ln2+ ions (Ln = rare earth metal) with unprecedented 4fn5d1 electron configurations has been explored to expand the unique chemistry possible with the rare earth elements. The isolation of unexpected reaction products is described as well as the discovery of a new divalent lanthanide system and the utilization of solvent-free mechanochemical synthesis for established rare earth organometallic species. In Chapter 1, the reactivity of the highly-reducing, air-, moisture-, and temperature-sensitive divalent lanthanide complexes [K(2.2.2-cryptand)][Cp'3Ln] (Ln = Y, La, Ce, Dy) is characterized by examining reactions with aromatic organic substrates of known reduction potential. Complexes of the 4fn5d1 Ln2+ ions reduce naphthalene and biphenyl within minutes to form a new class of reduced aromatic complexes, [K(2.2.2-cryptand)][Cp'2Ln(n4-C10H8)] (Ln = Y, La, Ce, Dy) and [K(2.2.2-cryptand)][Cp'2Y(n6-C6H5Ph)], respectively. The naphthalene reactions also produced the previously unobserved ligand redistribution products [K(2.2.2-cryptand)][Cp'4Ln] (Ln = Y, La), which show the effect of the lanthanide contraction on structure as the lanthanum complex has four n5-Cp' rings while yttrium has three n5-Cp' rings and one n1-Cp' ring.