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dc.contributor.authorAbraham, Mariham
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.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.description.advisorGregory Robinson
dc.description.committeeGregory Robinson
dc.description.committeeRobert Phillips
dc.description.committeeGeorge Majetich

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