Thomas JackmanOlaseni SodeWilliam Smith2018-03-062018-03-062017Smith, William . “Quantum Mechanical Investigation of the Inner Sphere Reduction of the [(NSSSN)Co(III)Cl+2] Cation and Its Analogs.” Acta Spartae, 2017. https://doi.org/10.48497/JZSB-EB70.http://hdl.handle.net/20.500.11868/324Recommended Citation: Smith, William . “Quantum Mechanical Investigation of the Inner Sphere Reduction of the [(NSSSN)Co(III)Cl+2] Cation and Its Analogs.” Acta Spartae, 2017. https://doi.org/10.48497/JZSB-EB70.The inner sphere pathway is an electron transfer (ET) mechanism that utilizes a bridging ligand to covalently link oxidant and reductant centers. The reductions of chloro-N-methyl-bis(5-amino- 3-thiapentyl)amine cobalt(III) [(NSNSN)Co(III)Cl+3] and chloro(1,11- diamino-3,6,9-trithiaundecane)cobalt(III) cation [(NSSSN)Co(III)Cl+2] by iron(II) via inner sphere ET have been shown experimentally to occur with rate constants more than 107 times faster than the nitrogen analog [(NNNNN)Co(III)Cl+2]. It has been hypothesized that this is due to non-bridging ligand effects. To test this hypothesis, the role of ground state electronic effects by the sulfur-containing ligands on the ET is investigated through the use of quantum chemistry methods. The non-bridging ligand effects were explored through the structural parameters of the cobalt complexes and by examining the LUMOs using both wavefunction theory (WFT) and density functional theory (DFT) methods. We show that the complexes containing sulfur atoms (NSSSN and NSNSN) display similar geometries. These are in contrast to the nitrogen analog (NNNNN) geometry, pointing towards a possible structural driving force in the rate constant difference.en-USinner sphere pathwayDepartment of Chemistry, Biochemistry and PhysicsResearch Subject Categories::NATURAL SCIENCESResearch Subject Categories::NATURAL SCIENCES::ChemistryArticlehttps://doi.org/10.48497/jzsb-eb70