Synthesis and Use of a Tetradentate Ligand With C4v Symmetry: 1alpha, 2alpha, 3alpha, 4alpha-Tetrahydroxy- 1beta, 2beta, 3beta, 4beta-Tetramethylcyclobutane
Kahle, Charles Franz, Ii
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https://hdl.handle.net/2142/70371
Description
Title
Synthesis and Use of a Tetradentate Ligand With C4v Symmetry: 1alpha, 2alpha, 3alpha, 4alpha-Tetrahydroxy- 1beta, 2beta, 3beta, 4beta-Tetramethylcyclobutane
Author(s)
Kahle, Charles Franz, Ii
Issue Date
1987
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Organic
Abstract
The synthesis and photochemistry is described for several enediol derivatives designed as possible precursors of a cyclobutane-based tetradentate ligand of C$\sb{\rm 4v}$ symmetry. A new synthetic dehydrogenation reaction to form carbon-carbon double bonds, using the in situ combination of potassium tert -butoxide and tert -butyl hypochlorite, is presented. The stereospecific intramolecular photodimerization of an enediol pyrophosphate is described. Hydrolysis of the photoproduct from this reaction gives $1\alpha,2\alpha,3\alpha,4\alpha$-tetrahydroxy-$1\beta,2\beta,3\beta,4\beta$-tetramethylcyclobutane, 1, a tetradentate ligand with C$\sb{\rm 4v}$ symmetry.
Evidence is presented for the first example of a monomeric square pyramidal 10-Te-4 species in solution, prepared by condensation of 1 with TeCl$\sb4$. A crystalline, cyclic pentamer of the 10-Te-4 tellurane is isolated by recrystallization of the monomeric 10-Te-4 species from acetonitrile. The X-ray structure of this pentamer is presented and discussed. This solution phase-solid phase equilibrium between monomer and pentamer is discussed in terms of the increase in entropy upon dissociation of the pentamer to monomer in solution.
The synthesis and ionophoric behaviour of the tetramethyl ether of 1 is presented. The tetramethyl ether is demonstrated to complex Li$\sp+$ and Na$\sp+$ ions in a 1:1 square pyramidal complex.
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