My work involved the synthesis, physical characterization, and studies into the chemical reactivity of various titanium, vanadium and chromium complexes of the macro-cyclic ligand (C(,22)H(,22)N(,4))('2-). These compounds were characterized using a variety of physical methods including ESR, NMR, IR Spectroscopy, cyclic voltammetry, and X-ray diffraction structure analysis, where appropriate. / The reaction of vanadyl acetate with the free ligand yields VO(C(,22)H(,22)N(,4)), which was structurally characterized. The vanadyl oxygen may subsequently be removed to give an extremely reactive (very water and oxygen sensitive) intermediate V((,22)H(,22)N(,4))Cl(,2)(.)HCl. The dihalovanadium (IV) complex reacts with a variety of small molecules including H(,2)S, NH(,3), and H(,2)O forming the sulfo, (mu)-nitrido dimer, and the starting vanadyl derivatives, respectively. / The analogous Ti(C(,22)H(,22)N(,4))Cl(,2) complex, prepared from TiCl(,4) and the free ligand, is less readily hydrolyzed than V(C(,22)H(,22)N(,4))Cl(,2)(.)HCl. An X-ray diffraction analysis of the structure revealed cis coordination of the two chloride ligands, leading to an approximate trigonal prismatic geometry of the inner coordination sphere. Several other complexes with cis geometry were prepared from a variety of ligands including catechol, 3,4dimercaptotoluene, oxalate, and 2,4pentanedione. A number of oxygen containing derivatives were isolated and characterized including the oxo compound TiO(C(,22)H(,22)N(,4)), the dimer O{Ti(C(,22)H(,22)N(,4))}(,2)X(,2), and a peroxo complex TiO(,2)(C(,22)H(,2)N(,4)). Two novel sulfur derivatives were prepared TiS(C(,22)H(,22)N(,4)) and TiS(,2)(C(,22)H(,22)N(,4)). The latter compound contains a coordinated persulfo ligand and is the only example of this type of coordination (that we are aware of) among the first row transition metals. Both TiS(,2)(C(,22)H(,22)N(,4)) and TiO(,2)(C(,22)H(,22)N(,4)) react with the atom transfer reagent P(C(,6)H(,5))(,3) to give S=P(C(,6)H(,5))(,3) and O=P(C(,6)H(,5))(,3), respectively. / Studies of chromium reaction chemistry in this ligand are currently being completed. The chromium chemistry is complicated by sensitivity to H(,2)O and O(,2), leading to irreversibly oxidized and decomposition products. The reaction of anhydrous CrCl(,3) with free ligand, in the presence of Zn, produces Cr(C(,22)H(,22)N(,4))(S)Cl where S is a coordinated solvent molecule, typically CH(,3)CN. Excess pyridine can be displaced both the solvent and the coordinated chloride. A bis-methoxy complex Cr(C(,22)H(,22)N(,4))(OMe)(,2) is prepared by the action of NaOMe or Cr(C(,22)H(,22)N(,4))(CH(,3)CN)Cl. A novel product in whichCH(,3)CN has added at the methine carbon atom of the pentanedionato / chelate ring to produce a pentadentate macrocyclic ligand can beisolated as the SCN('-) adduct,(' )Cr(C(,22)H(,22)N(,4))(-C=N)NCS. / (VBAR) / CH(,3) / Source: Dissertation Abstracts International, Volume: 43-08, Section: B, page: 2547. / Thesis (Ph.D.)--The Florida State University, 1982.
| Identifer | oai:union.ndltd.org:fsu.edu/oai:fsu.digital.flvc.org:fsu_74916 |
| Contributors | LADD, JUDITH ANN., Florida State University |
| Source Sets | Florida State University |
| Detected Language | English |
| Type | Text |
| Format | 191 p. |
| Rights | On campus use only. |
| Relation | Dissertation Abstracts International |
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