Show simple item record

dc.contributor.authorAbraham, Mariham
dc.date.accessioned2014-03-04T21:04:53Z
dc.date.available2014-03-04T21:04:53Z
dc.date.issued2013-08
dc.identifier.otherabraham_mariham_201308_phd
dc.identifier.urihttp://purl.galileo.usg.edu/uga_etd/abraham_mariham_201308_phd
dc.identifier.urihttp://hdl.handle.net/10724/28956
dc.description.abstractThe syntheses and molecular structures of carbene-stabilized arsenic derivatives of AsCl3 (L1:AsCl3 (1); L1: = :C{N(2,6-iPr2C6H3)CH}2), and As2 (L1:As–As:L1 (2)), are presented herein. The potassium graphite reduction of 1 afforded the carbene-stabilized diarsenic complex, 2. Notably, compound 2 is the first Lewis base stabilized diatomic molecule of the Group 13–15 elements, in the formal oxidation state of zero, in the fourth period or lower of the Periodic Table. Compound 2 contains one As–As σ-bond and two lone pairs of electrons on each arsenic atom. In an effort to study the chemistry of the electron-rich compound 2, it was combined with an electron-deficient Lewis acid, GaCl3. The addition of two equivalents of GaCl3 to 2 resulted in one-electron oxidation of 2 to give [L1:As As:L1]•+[GaCl4]– (6•+[GaCl4]–). Conversely, the addition of four equivalents of GaCl3 to 2 resulted in two- electron oxidation of 2 to give [L1:As=As:L1]2+[GaCl4–]2 (62+[GaCl4–]2). Strikingly, 6•+ represents the first arsenic radical to be structurally characterized in the solid state. The research project also explored the reactivity of carbene-stabilized disilicon, (L1:Si=Si:L1 (7)), with borane. The reaction of 7 with BH3•THF afforded two unique compounds: one containing a parent silylene (:SiH2) unit (8), and another containing a three-membered silylene ring (9). Notably, 8 is the first example of a “push–pull” stabilized parent silylene, while 9 is the first example of a three-membered cyclic silylene, both of which are persistent under ambient conditions.
dc.languageeng
dc.publisheruga
dc.rightspublic
dc.subjectarsenic, N-heterocyclic carbene, diatomic, gallium, metal–metal bonds, main-group, oxidation, oxidation-state, “push-pull”, radical,reduction, silicon, silylene, sterically demanding ligands
dc.titleThe chemistry of carbene-stabilized main group diatomic allotropes
dc.typeDissertation
dc.description.degreePhD
dc.description.departmentChemistry
dc.description.majorChemistry
dc.description.advisorGregory Robinson
dc.description.committeeGregory Robinson
dc.description.committeeRobert Phillips
dc.description.committeeGeorge Majetich


Files in this item

FilesSizeFormatView

There are no files associated with this item.

This item appears in the following Collection(s)

Show simple item record