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UNITING EXPERIMENT AND THEORY: THE DEVELOPMENT AND APPLICATION OF THEORETICAL MOLECULAR MODELS TO NICKEL(II)TRIS(OXIME)AMINE COMPLEXES

JONES, REBECCA MARIE
http://rave.ohiolink.edu/etdc/view?acc_num=ucin1084753268

Abstract Details

2004, PhD, University of Cincinnati, Arts and Sciences : Chemistry.
Using density-functional theory and vibrational spectroscopy, various theoretical models are evaluated for application to Ni(TRISOXH 3 )Cl 2 , the precursor to a novel oxygen-activating complex. Geometry optimizations and frequency calculations were performed using DFT and compared to the X-ray crystal structure and vibrational spectra. The best geometry resulted from B3LYP/6-31G(d) & 6-311++G** with only a 1.0% average deviation from experimental bond distances not influenced by intermolecular interactions. Nickel complexes with isotope substituted TRISOXH 3 ligands were synthesized. The isotope shifts in the vibrational spectra were observed and compared to the predicted shifts to facilitate the assignment of 28 normal modes. A modified wavenumber linear scaling procedure was applied to the assigned theoretical wavenumbers and yielded a 3-fold improvement in absolute deviation from experimental frequencies over the unscaled values. Further application of this model is applied to complexes of the form Ni(TRISOXH 3 )X 2 where X is fluoride, bromide, iodide, methanol, and/or water to evaluate ligand effects on metal-oxime interactions. Complexes where X is bromide or iodide exhibited very similar geometries and vibrational frequencies to Ni(TRISOXH 3 )Cl 2 , while significant structural and electronic differences were observed when X is water or fluoride.
Dr. Michael Baldwin (Advisor)
167 p.
Chemistry, Inorganic

Recommended Citations

Citations

  • JONES, R. M. (2004). UNITING EXPERIMENT AND THEORY: THE DEVELOPMENT AND APPLICATION OF THEORETICAL MOLECULAR MODELS TO NICKEL(II)TRIS(OXIME)AMINE COMPLEXES [Doctoral dissertation, University of Cincinnati]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1084753268

    APA Style (7th edition)

  • JONES, REBECCA. UNITING EXPERIMENT AND THEORY: THE DEVELOPMENT AND APPLICATION OF THEORETICAL MOLECULAR MODELS TO NICKEL(II)TRIS(OXIME)AMINE COMPLEXES. 2004. University of Cincinnati, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=ucin1084753268.

    MLA Style (8th edition)

  • JONES, REBECCA. "UNITING EXPERIMENT AND THEORY: THE DEVELOPMENT AND APPLICATION OF THEORETICAL MOLECULAR MODELS TO NICKEL(II)TRIS(OXIME)AMINE COMPLEXES." Doctoral dissertation, University of Cincinnati, 2004. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1084753268

    Chicago Manual of Style (17th edition)

ucin1084753268
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© 2004, all rights reserved.
This open access ETD is published by University of Cincinnati and OhioLINK.
Release 3.2.12