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dc.contributor.advisorHall, Michael B
dc.creatorKritikou, Stella
dc.date.accessioned2015-01-09T19:58:22Z
dc.date.available2016-05-01T05:31:03Z
dc.date.created2014-05
dc.date.issued2014-02-27
dc.date.submittedMay 2014
dc.identifier.urihttps://hdl.handle.net/1969.1/152530
dc.description.abstractDensity functional theory results of the electronic structure of an iridium sulfide, Ir_(2)S_(2)(PPh_(3))_(4) (2), are presented here, along with a discussion of the reaction mechanism of dihydrogen activation on this sulfide. This Ir (II) sulfide shows unusual reactivity binding two equivalents of H_(2). The first reaction was believed to be a homolytic cleavage of one H_(2), between the two iridium centers, which would produce the dihydride complex Ir_(2)(PPh_(3))_(2)H_(2)(µ-S)_(2) (3), while the second-product was believed to arise from heterolytic cleavage by (3) of a second H_(2), between an iridium and a bridging-sulfur atom, which would produce Ir_(2)(µ-S)(µ-SH)(µ-H)H_(2)(PPh_(3))_(4) (4). Previously published crystal structures on (2) and (3) suggest that the there is a strong metal-metal bond in the Ir(II) d7 dimer, (2), and that this bond is surprisingly preserved in the first H_(2) cleavage product, (3). We investigated the activation of H_(2) by this Ir(II) complex, and the corresponding model complex Ir_(2)(µ-S)_(2)(PH(3))_(4), in order to determine the details of this pathway. Our proposed mechanism suggests that the activation of the first equivalent of hydrogen can be either heterolytic or hemolytic, leading to a species with a bridging hydride Ir_(2)H(µ-S)_(2)(µ-H)(PPh_(3))_(4) (3-brid) in which the metal-metal bond is preserved, while the second activation appears to be a heterolytic activation, which produces the final product (4).en
dc.format.mimetypeapplication/pdf
dc.language.isoen
dc.subjectTheoretical Chemistry, Inorganic Chemistry, Quantum Chemistry, Density Functional Theory, Hydrogen Activationen
dc.titleTheoretical Investigation of Iridium (II) Sulfides Ir2(μ-S)2(PH3)4 AND Ir2(μ-S)2(PPh3)4en
dc.typeThesisen
thesis.degree.departmentChemistryen
thesis.degree.disciplineChemistryen
thesis.degree.grantorTexas A & M Universityen
thesis.degree.nameMaster of Scienceen
thesis.degree.levelMastersen
dc.contributor.committeeMemberYeager, Danny L
dc.contributor.committeeMemberNorth, Simon W
dc.contributor.committeeMemberNanopoulos, Dimitri
dc.type.materialtexten
dc.date.updated2015-01-09T19:58:22Z
local.embargo.terms2016-05-01
local.etdauthor.orcid0000-0003-0080-9849


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