Chemical and electrochemical oxidations of tris(3,5-di-tert-butylphenyl)phosphine. High Z’ crystal structures and conformational effects associated with bulky meta substituents

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dc.contributor.authorGuimaraes, Ivelise Dimbarre Lao
dc.contributor.authorGarcia, Jarem Raul
dc.contributor.authorWohnrath, Karen
dc.contributor.authorBoeré, René T.
dc.date.accessioned2019-05-12T20:48:47Z
dc.date.available2019-05-12T20:48:47Z
dc.date.issued2018
dc.descriptionAccepted peer reviewed author manuscript. It may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Version.en_US
dc.description.abstractSynthesis and single crystal X-ray diffraction structures of (3,5-tBu2-C6H3)3P, (3,5-tBu2-C6H3)3PO∙H2O, (3,5-tBu2C6H3)3PS and (3,5-tBu2-C6H3)3PSe are reported. The structure of (3,5-tBu2-C6H3)3P has Z' = 4, with both M and P enantiomers of a helical conformation and a conformation with one flat ring in the same lattice. The pyramidality index, ∑{CPC}, is smaller for the helical compared to the flat conformers. All four have structures that are more pyramidal than the corresponding Ph3P(E) derivatives, which is attributed to stronger intramolecular dispersion forces. The oxide crystallizes with Z' = 2 as a water-bridged dimer that is the most separated such dimer amongst 26 known structures, providing evidence for a distal (or perimeter) steric effect. Cyclic voltammetry in CH3CN/[nBu4N][ClO4] indicated anodic peak potentials of +0.785 V for (3,5tBu2-C6H3)3P, +0.745 for (3,5-Me2-C6H3)3P, +0.735 V for (4-MeO-3,5-Me2-C6H3)3P and +0.535 V for (4-MeOC6H3)3P, all relative to Fc+/0. On this scale, Ph3P oxidizes at +1.04 V. The unexpectedly high oxidation potentials for the first three phosphines is attributed to a more pyramidal structure resulting in lowering of the HOMO energy compared to expectations from Hammett constants and 1J(P,Se) NMR coupling constants.en_US
dc.description.peer-reviewYesen_US
dc.identifier.citationGuimaraes, I. D. L., Garcia, J. R., Wohnrath, K., & Boeré, R. T. (2018). Chemical and electrochemical oxidations of tris(3,5-di-tert-butylphenyl)phosphine: High Z’ crystal structures and conformational effects associated with bulky meta substituents. European Journal of Inorganic Chemistry, 3606-3614. DOI: 10.1002/ejic.201800656en_US
dc.identifier.urihttps://hdl.handle.net/10133/5353
dc.language.isoen_USen_US
dc.publisher.departmentDepartment of Chemistry and Biochemistryen_US
dc.publisher.doi
dc.publisher.facultyArts and Scienceen_US
dc.publisher.institutionUniversidade Estadual de Ponta Grossaen_US
dc.publisher.institutionUniversity of Lethbridgeen_US
dc.publisher.urlhttps://doi.org/10.1002/ejic.201800656
dc.subjectTriarylphosphaneen_US
dc.subjectDonor strengths from voltammetryen_US
dc.subjectRacemization of propeller moleculesen_US
dc.subjectLondon dispersion forcesen_US
dc.subjectEmpirical dispersion correctionsen_US
dc.subjectPhosphane ligandsen_US
dc.subjectRedox chemistryen_US
dc.subjectStructure elucidationen_US
dc.subject.lcshOxidation-reduction reaction
dc.titleChemical and electrochemical oxidations of tris(3,5-di-tert-butylphenyl)phosphine. High Z’ crystal structures and conformational effects associated with bulky meta substituentsen_US
dc.typeArticleen_US
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