Spectroscopic and Computational Analysis of Rare Earth and Actinide Complexes in Unusual Coordination Environments and Oxidation States
Author | : Megan E. Fieser |
Publisher | : |
Total Pages | : 416 |
Release | : 2015 |
ISBN-10 | : 132196420X |
ISBN-13 | : 9781321964202 |
Rating | : 4/5 (0X Downloads) |
Download or read book Spectroscopic and Computational Analysis of Rare Earth and Actinide Complexes in Unusual Coordination Environments and Oxidation States written by Megan E. Fieser and published by . This book was released on 2015 with total page 416 pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation describes the use of spectroscopic and computational methods to understand new classes of rare earth and actinide coordination complexes. In Chapters 1 and 2, the use of UV-vis spectroscopy and density functional theory (DFT) to understand a rare form of photochemical activation of rare earth mixed-ligand tris(cyclopentadienyl) complexes, [formula], and metallocene allyl complexes, [formula] is described. The photochemistry involves a ligand-based reduction in a trivalent rare earth complex that generates a reducing system powerful enough to reduce dinitrogen. Chapter 3 describes the use of Raman spectroscopy to understand bond lengths in reduced dinitrogen rare earth complexes, [formula], and analyze the degree of dinitrogen reduction based on the ancillary ligands. Chapter 4 describes the power of NMR spectroscopy to characterize complicated mixtures of heterobimetallic bridging hydride complexes, [formula], and tuckover hydride complexes, [formula]. DFT was used to investigate the metal site preferences in these complexes. Chapters 5 through 10 describe different techniques to understand the first examples of molecular rare earth and actinide tris(cyclopentadienyl) complexes in the formal +2 oxidation state, [formula], lanthanides, Th, U). DFT is used to describe the configuration of these complexes as 4d1 for Y, [formula] for 10 lanthanides and [An3+]6d1 for Th and U (Chapter 5 and 6). UV-vis spectroscopy was used to distinguish between different electron configurations of Ln2+ complexes (Chapter 7). Magnetic susceptibility measurements characterize two Ln2+ complexes to have record high single-ion magnetic moments (Chapter 8). Ligand and metal edge X-ray absorption spectroscopy were used to analyze the oxidation state of the metals (Chapter 9). Reactivity of cyclooctatetraene with Ln2+ complexes is described in Chapter 10. Chapter 11 presents the synthesis of new Ln3+ and Ln2+ complexes, using a tris(aryloxide)arene coordination environment. Chapter 12 describes the use of DFT to predict new coordination environments that could allow the stabilization of the +2 oxidation state for the rare earths and actinides.