Theoretical Investigation of Iridium (II) Sulfides Ir2(?-S)2(PH3)4 AND Ir2(?-S)2(PPh3)4
| dc.contributor | Hall, Michael B | |
| dc.creator | Kritikou, Stella | |
| dc.date.accessioned | 2016-05-01T05:31:03Z | |
| dc.date.accessioned | 2017-04-07T20:08:40Z | |
| dc.date.available | 2016-05-01T05:31:03Z | |
| dc.date.available | 2017-04-07T20:08:40Z | |
| dc.date.created | 2014-05 | |
| dc.date.issued | 2014-02-27 | |
| dc.description.abstract | Density 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)(?-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)(?-S)(?-SH)(?-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)(?-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(?-S)_(2)(?-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). | |
| dc.identifier.uri | http://hdl.handle.net/1969.1/152530 | |
| dc.language.iso | en | |
| dc.subject | Theoretical Chemistry, Inorganic Chemistry, Quantum Chemistry, Density Functional Theory, Hydrogen Activation | |
| dc.title | Theoretical Investigation of Iridium (II) Sulfides Ir2(?-S)2(PH3)4 AND Ir2(?-S)2(PPh3)4 | |
| dc.type | Thesis |