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Measuring and Leveraging Electrostatic Effects in a Charged Phosphine

submitted on 14.12.2020, 14:39 and posted on 15.12.2020, 13:22 by Andrew J. McNeece, Margaret L. Kelty, Alexander S. Filatov, John Anderson
Local electric fields have recently been investigated for optimizing reactivity in synthetic systems. However, disentangling the relative contributions of inductive (through-bond) and electrostatic (through-space) effects in molecular systems has been a long-standing challenge. To understand the interplay of these effects and leverage electrostatic influences for enhanced reactivity, we have synthesized a distally charged phosphine, Ph2PCH2BF3, and studied the effect of the charged trifluoroborate group on its donor properties and reactivity. This charged phosphine displays solvent-dependent changes in donor strength as measured by the JP-Se of the corresponding phosphine selenide. The variation with solvent dielectric illustrates a significant electrostatic component to the donor strength. Computations further support the importance of electrostatic contributions and highlight the effect of charge position and orientation. Finally, this charged group also greatly accelerates C–F oxidative addition reactivity in Ni complexes, experimentally
verifying recent theoretical predictions. These results show that covalently bound charged functionalities can exert a significant electrostatic influence even under common solution phase reaction conditions.


R35 GM133470


DGE- 1746045




Email Address of Submitting Author


University of Chicago


United States

ORCID For Submitting Author


Declaration of Conflict of Interest

There are no conflicting interests.