TITLE:
One-Electron-Addition to Pentavalent Phosphorus with the Phosphorus-Chlorine Bond as Acceptor Introducing a Fundamental Distinction in Substitution Mechanism between SN2(P) and SN2(C)
AUTHORS:
Henk M. Buck
KEYWORDS:
Pentavalent Phosphorus and Carbon Compounds, σ*-Electron-Addition, Single-Crystal Electron Spin Resonance (ESR), Model and Ab Initio Calculations, Differences in SN2(C) vs. SN2(P) Mechanism
JOURNAL NAME:
Open Journal of Physical Chemistry,
Vol.9 No.3,
August
30,
2019
ABSTRACT: An electron-addition, under single-crystal
conditions, to pentavalent phosphorus compounds as Cl-P (=O, S) Y, Z with the P-Cl bond as electron-accepting group, is selected as an
additional model for SN2(P) like reactions. It is demonstrated that the geometric information stored in the tetrahedral
configuration (substrate) can be transmitted in the corresponding trigonal
bipyramidal (TBP) state for nucleophilic substitution. In this article, we
focus on these specific mechanistic aspects of carbon and phosphorus. We
consider our study as a contribution to the significance of these (bio)chemical
intermediates.