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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Guimaraes, Ivelise Dimbarre Lao
Garcia, Jarem Raul
Wohnrath, Karen
Boeré, René T.
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Synthesis 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.
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Triarylphosphane , Donor strengths from voltammetry , Racemization of propeller molecules , London dispersion forces , Empirical dispersion corrections , Phosphane ligands , Redox chemistry , Structure elucidation
Guimaraes, 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.201800656