The objective of this dissertation was to test the hypothesis that constrained ligand environments can influence the stability of aluminum-carbon bonds. The synthesis and characterization of a variety of organo-aluminum complexes of tetradentate Schiff-base ligands with varying degrees of backbone flexibility is presented. The reaction of trialkylaluminum compounds with tetradentate Schiff-base ligands having two replaceable hydrogen atoms (SALEN, SALPN, SALOPHEN, and ACEN) proceeds smoothly to yield complexes of the type Al(L)R, L = Shiff-base ligand. The stability of the aluminum carbon bond in these complexes increases with increasing ligand flexibility and is attributed to kinetic rather than thermodynamic factors. When constraints are released more by replacing the tetradentate ligand with two molecules of bidentate 8-quinolinol, complexes of the desired stoichiometry are unstable and rapidly disproportionate. The complex isolated, Al(8-quinolinol)(C(,2)H(,5))(,2) (,2) was high reactivity and bears little resemblance in its properties to those of the mono-alkyl Schiff-base complexes. The dimeric nature was inferred from ('1)H NMR studies and confirmed by single crystal x-ray structure analyses. In related studies with dialkylzinc compounds, adduct formation was observed with Ni SALEN through the two oxygen atoms of the SALEN ligand. However, this complex is highly reactive to both air and moisture. Additional studies, largely x-ray crystallographic in nature, were used to characterize a heterobridged (mu)-oxo iron-silicon compound as well as the first low-spin (mu)-oxo Fe(III) phthalocyanine complex. / Source: Dissertation Abstracts International, Volume: 48-03, Section: B, page: 0751. / Thesis (Ph.D.)--The Florida State University, 1987.
| Identifer | oai:union.ndltd.org:fsu.edu/oai:fsu.digital.flvc.org:fsu_76088 |
| Contributors | DZUGAN, SHARLENE JOY., Florida State University |
| Source Sets | Florida State University |
| Detected Language | English |
| Type | Text |
| Format | 231 p. |
| Rights | On campus use only. |
| Relation | Dissertation Abstracts International |
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