Quantum mechanical investigation of the inner sphere reduction of the [(NSSSN)Co(III)Cl+2] cation and its analogs
Date
2017
Authors
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Publisher
College of Natural and Health Sciences, The University of Tampa
Abstract
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.
Description
Recommended 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.
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Keywords
inner sphere pathway, Department of Chemistry, Biochemistry and Physics, Research Subject Categories::NATURAL SCIENCES, Research Subject Categories::NATURAL SCIENCES::Chemistry
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.