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Measuring and Leveraging Electrostatic Effects in a Charged Phosphine

preprint
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.

Funding

R35 GM133470

DGE-1144082

DGE- 1746045

FG-2019-11497

3M NTFA

History

Email Address of Submitting Author

jsanderson@uchicago.edu

Institution

University of Chicago

Country

United States

ORCID For Submitting Author

0000-0002-0730-3018

Declaration of Conflict of Interest

There are no conflicting interests.

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