One-Electron-Addition to Pentavalent Phosphorus with the Phosphorus-Chlorine Bond as Acceptor Introducing a Fundamental Distinction in Substitution Mechanism between S&amp;lt;sub&amp;gt;N&amp;lt;/sub&amp;gt;2(P) and S&amp;lt;sub&amp;gt;N&amp;lt;/sub&amp;gt;2(C)

Henk M Buck

doi:10.4236/ojpc.2019.93010

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.

Highlights

Our research has correspondence with nucleophilic phosphorus inversion using the smallest nucleophilic agent (e−)
It is demonstrated that the geometric information stored in the tetrahedral configuration can be transmitted in the corresponding trigonal bipyramidal (TBP) state for nucleophilic substitution
The x-ray irradiation of the 2R, 4S, 5R (1) and 2S, 4S, 5R (2) substrates was carried out under single-crystal conditions and low temperature at 77 K resulting in a high yield and corresponding strong electron spin resonance (ESR) absorptions at 105 K of 1a and a very weak ESR signal of 2a suggesting the impact of geometric inter-molecular interactions

Summary

Introduction

The introduction of specific group-sites in organic systems for accommodation of various modes of bonding focused on different reaction types has been described by us using a variety of (theoretical) models. In the most ideal (tetrahedral) configuration, the ratio number for the TS i.e., the ratio between the apical distance and the corresponding bond length in the initial state is 1.333 (=1-cos 109.47 ̊) or 1 + n/12 with n = 4, the number of electrons. These ratio numbers are indicated as R(d), R(θ), and R(n), respectively. Using the expression R(n) = 1 + n/12 with n the number of electrons in the three-center bonding for the transition states of both conversions results in four and three electrons, respectively.

Experimental Results and Discussion

Method

Conclusion