The neighboring tin effect: The synthesis and electrochemical analysis of α-stannyl thioethers.

Persistent Link:
http://hdl.handle.net/10150/186044
Title:
The neighboring tin effect: The synthesis and electrochemical analysis of α-stannyl thioethers.
Author:
Martin, Amanda Marie.
Issue Date:
1992
Publisher:
The University of Arizona.
Rights:
Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.
Abstract:
The interaction between the 3p orbital on a sulfur atom, specifically in 1,3-dithianes, with the sigma orbital of a carbon-tin bond is investigated. It appears that the ability of these two orbitals to interact effectively depends on the geometry of the orbitals concerned, maximized when coplanarity is possible. This interaction is monitored via cyclic voltammetric experiments, where the oxidation potential of 1,3-dithiane is 1.18 V, while the potential drops dramatically to 0.19 for 2,2-bis-(trimethylstannyl)-1,3-dithiane. Anancomerically locked dithianes, where ring-flipping of the dithiane ring is prohibited, were also investigated. Various NMR experiments, including variable temperature ¹³C NMR and nOe were performed to determine the conformation in solution of many of these compounds. This phenomenon was briefly examined via photoelectron spectroscopy, where a similar decrease in the ionization potential of bis-stannyl-1,3-dithiane suggests that the observed oxidation potentials do not arise from any surface or heterogeneity effect, and instead arise from an inherent property of the molecule concerned.
Type:
text; Dissertation-Reproduction (electronic)
Keywords:
Dissertations, Academic.; Chemistry, Organic.
Degree Name:
Ph.D.
Degree Level:
doctoral
Degree Program:
Chemistry; Graduate College
Degree Grantor:
University of Arizona
Committee Chair:
Glass, Richard S.

Full metadata record

DC FieldValue Language
dc.language.isoenen_US
dc.titleThe neighboring tin effect: The synthesis and electrochemical analysis of α-stannyl thioethers.en_US
dc.creatorMartin, Amanda Marie.en_US
dc.contributor.authorMartin, Amanda Marie.en_US
dc.date.issued1992en_US
dc.publisherThe University of Arizona.en_US
dc.rightsCopyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.en_US
dc.description.abstractThe interaction between the 3p orbital on a sulfur atom, specifically in 1,3-dithianes, with the sigma orbital of a carbon-tin bond is investigated. It appears that the ability of these two orbitals to interact effectively depends on the geometry of the orbitals concerned, maximized when coplanarity is possible. This interaction is monitored via cyclic voltammetric experiments, where the oxidation potential of 1,3-dithiane is 1.18 V, while the potential drops dramatically to 0.19 for 2,2-bis-(trimethylstannyl)-1,3-dithiane. Anancomerically locked dithianes, where ring-flipping of the dithiane ring is prohibited, were also investigated. Various NMR experiments, including variable temperature ¹³C NMR and nOe were performed to determine the conformation in solution of many of these compounds. This phenomenon was briefly examined via photoelectron spectroscopy, where a similar decrease in the ionization potential of bis-stannyl-1,3-dithiane suggests that the observed oxidation potentials do not arise from any surface or heterogeneity effect, and instead arise from an inherent property of the molecule concerned.en_US
dc.typetexten_US
dc.typeDissertation-Reproduction (electronic)en_US
dc.subjectDissertations, Academic.en_US
dc.subjectChemistry, Organic.en_US
thesis.degree.namePh.D.en_US
thesis.degree.leveldoctoralen_US
thesis.degree.disciplineChemistryen_US
thesis.degree.disciplineGraduate Collegeen_US
thesis.degree.grantorUniversity of Arizonaen_US
dc.contributor.chairGlass, Richard S.en_US
dc.contributor.committeememberMash, Eugeneen_US
dc.contributor.committeememberGervay, Jacquelynen_US
dc.contributor.committeememberWigley, Daviden_US
dc.contributor.committeememberMiller, Walteren_US
dc.identifier.proquest9307703en_US
dc.identifier.oclc714143135en_US
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